Method for controlling insects with tetrasubstituted organotin compounds

ABSTRACT

Tetrasubstituted organotin compounds, which are useful for controlling insects and other pests, are disclosed. Many of these organotin compounds are new compounds.

This application is a continuation-in-part of application Ser. No.536,678, filed on Dec. 26, 1974 now abandoned.

RELATED CASE

The compounds in which X is --SO₂ R₁ and in which R₁ is ##STR1## J beingselected from the group consisting of linear and branched alkyl having 1to 20 carbon atoms, cycloaliphatic having 4 to 6 carbon atoms andstraight chain and branched alkenyl having 2 to 20 carbon atoms and mbeing an integer from 1 to 3, are claimed in copending application ofStrunk and Hubbard, Ser. No. 641,060, filed concurrently herewith nowU.S. Pat. No. 3,976,672.

This invention relates to tetrasubstituted organotin compounds which areuseful for controlling insects and pests and as herbicides. Many ofthese tetrasubstituted organotins are new compounds.

BACKGROUND OF THE INVENTION

Some tetrasubstituted organotin compounds are known from the prior art.For example, British Patent No. 966,813 to Ziegler discloses a methodfor obtaining tetrasubstituted organotin compounds useful as highpolymers, but no suggestion is made in this patent that these compoundsmight find utility in controlling insects and other pests or be usefulas herbicides and fungicides.

Other substituted organotin compounds are also known from the prior artfor use as pesticides, acaricides bactericides, fungicides andherbicides or as protective coatings.

For example, U.S. Pat. No. 3,642,845 to Ramsden discloses bistrialkyltincompounds of the formula

    (R).sub.3 SnR'Sn(R).sub.3

wherein R is an alkyl group and R' is a hydrocarbon di-radical having aminimum of 8 carbon atoms. These compounds exhibit systemic pesticidalactivity, particularly against lepidoptera insect larvae, such as theSouthern army worm.

Another example is U.S. Pat. No. 3,206,489 to Stamm et al. whichdiscloses tetrasubstituted tin compounds of the general formula ##STR2##wherein R₁, R₂, and R₃ and R₄ can be alkyl radicals having from 1 to 12carbon atoms and an aromatic hydrocarbon radical provided one of the Rsubstituents is an alkyl radical terminating in a lower aliphaticthioacid group which is characterized by the presence of a thiocarboxylfunction. These compounds are indicated as being useful as herbicides.

A further example in U.S. Pat. No. 3,591,614 to Bublitz which disclosescompounds of the formula ##STR3## wherein R is 2-cyanoethyl,2-carboxyethyl, or 2-carb(lower)alkoxyethyl group. These substitutedethyl derivatives of tricyclohexyltin are indicated as being useful asacaricides for the control of mites and ticks.

An additional U.S. Pat. No. 3,641,037 to Bublitz discloses compounds ofthe formula ##STR4## wherein R is 2-furyl, 2-pyridyl, 3-pyridyl,1-indenyl, or 2-(2-pyridyl)ethyl, these compounds being useful aspesticides, particularly for the control of mites and ticks.

A further example is German patent No. 2,231,814 to Peterson whichdiscloses compounds of the formula

    (R).sub.3 SnCH.sub.2 -X

wherein X is alkyl- or arylsulfonyl, alkyl- or arylthio or dialkylaminoand R is alkyl of from 1 to 14 carbon atoms. These compounds aredisclosed as being useful in protective coatings against bacteria,fungi, termites and barnacles.

Peterson, in U.S. Pat. No. 3,725,446, claims some of the same compounds,R-S-CH₂ -Sn-R₃ ', where R is alkyl of from 1 to 14 carbon atoms, aryl orsubstituted aryl, and R' is alkyl of 1 to 14 carbon atoms. Thesecompounds are said to have pre-emergent and post-emergent herbicidalactivity.

Another German Patent No. 2,106,040 (U.S. Pat. No. 3,784,580 toPeterson) also discloses compounds of the formula (R)₃ SnCH₂ -X whereinX is alkylsulfonyl, arylsulfonyl or dialkylsulfamoyl, the compoundsbeing useful as pesticides and acaricides.

The compounds disclosed in the two German patents discussed immediatelyabove differ from the compounds of this invention in that the "X" moietyis linked to the tin atom by a single methylene diradical instead of bya diradical having at least 2 carbon atoms.

Peterson has authored a paper, "Preparation and Reactions of someSulfur-Substituted Tetraorganotin Compounds," J. Organometal Chem. 26,215-223 (1971). The following paragraph appears at page 218:

"[(Phenylsulfonyl)methyl] tributyltin [(IV)] was found to be unreactivetoward carbon dioxide and oxygen at room temperature, while exposure ofa thin layer of (IV) to air resulted in ca. 50% decomposition to phenylmethyl sulfone and tributyltin oxide within four days. These findings,when regarded in conjunction, are in accord with hydrolysis beingresponsible for the air sensitivity of (IV)."

Peterson, in U.S. Pat. No. 3,794,670, has covered a method for preparing(organosulfonylmethyl) triorganotin compounds by reacting a triorganotinamine and an organosulfonylmethyl compound.

Ayrey et al. have published a paper, J. Organometal. Chem. 35, 105-109(1972), in which they deal with the preparation of3-(trialkylstannyl)propyl aryl sulfides, R₃ SnCH₂ CH₂ CH₂ SR'. Noutility is stated for these compounds.

Koopmans, in U.S. Pat. No. 3,031,483, discloses compounds of thestructure ##STR5## in which R₁, R₂ and R₃ may be the same or differentand represent alkyl groups with 1-12 carbon atoms, phenyl groups orhalophenyl groups, and Q represents one of a number of groups, including##STR6## These compounds have fungicidal and bactericidal properties.

THE INVENTION

The novel organotin compounds of this invention are tetrasubstituted tincompounds having the general formula ##STR7## wherein: R' is hydrogen,hydroxyl, methyl or ethoxy;

X is (a) --SO₂ R₁, R' being hydrogen, and wherein R₁ is a straight chainor branched alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl,phenyl or phenyl substituted with one or more groups which may be thesame or different and which may be alkoxy having 1 to 8 carbon atoms,phenoxy, alkylthio having 1 to 8 carbon atoms, halogen, nitro, acetyl,acetamido, carboxy, alkoxycarbonyl, carbamoyl, cyano, hydroxy,trifluoromethyl, benzyl, naphthyl or norbornyl; naphthyl, biphenylyl,piperidinoethylmethiodide, --R₂ Sn(CH₃)₃ wherein R₂ is polymethylenehaving from 2 to 11 carbon atoms, --R₄ SO₂ R₅ Sn(CH₃)₃ wherein R₄ isethylene and R₅ is as defined for R₂ above;

(b) --OR₇, R' being hydrogen, and wherein R₇ is a straight chain orbranched alkyl having 8 to 16 carbon atoms, aryl, alkoxyaryl, alkaryl,haloaryl, N,N-dialkylaminoalkyl, --R₈ Sn(CH₃)₃ wherein R₈ is alkylenehaving 2 to 11 carbon atoms, cycloaliphatic having 4 to 6 carbon atoms,tetrahydro-1,1-dioxo-3-thienyl;

(c) --SR₁₀, R' being hydrogen, and wherein R₁₀ is a straight chain orbranched alkyl having 1 to 16 carbon atoms, phenyl, chlorophenyl,t-butylphenyl or --R₂ Sn(CH₃)₃ ;

(d) --COR₁₁, R' being hydrogen, and wherein R₁₁ is --NHR₁₂ wherein R₁₂is a straight chain or branched alkyl having 1 to 12 carbon atoms oraryl; --NHCH₂ OH; --NHNH₂ ; --NHCH₂ NHCOR₂ Sn(CH₃)₃ ; --OR₁₃ wherein R₁₃is a straight chain or branched alkyl having 8 to 15 carbon atoms;--(CH₂)_(m) OH, wherein m is an integer from 2 to 4; --(CH₂)_(p) N(R₁₄)₂wherein p is an integer from 2 to 4 and R₁₄ is a straight chain orbranched alkyl having 1 to 5 carbon atoms; --(CH₂)_(q) OCOR₂ Sn(CH₃)₃wherein q is as defined for p above; --(CH₂)_(s) N⁺ (CH₃)₃ I⁻ wherein sis as defined for p above;

(e) --NHCONH₂, R' being hydrogen;

(f) --NHCSNH₂ ; R' being hydrogen;

(g) 1-imidazolyl, R' being hydrogen;

(h) N-2-oxopyrrolidinyl, R' being hydrogen;

(i) --OCOR₁₇, R' being hydrogen, and wherein R₁₇ is --NHR₁₈ wherein R₁₈is a straight chain or branched alkyl having 1 to 5 carbon atoms;2-furyl; and --O(CH₂)_(t) Sn(CH₃)₃ wherein t is from 2 to 11;

(j) --PO(OR₂₀)₂, R' being hydrogen or ethoxy, and wherein R₂₀ is astraight chain or branched alkyl having 1 to 5 carbon atoms;

(k) tetrahydro-1,1-dioxo-2-thenyl, R' being hydroxyl;

(l) --Si(OR₂₁)₃, R' being hydrogen, and wherein R₂₁ is a straight chainor branched alkyl having 1 to 5 carbon atoms; ##STR8## R' beinghydrogen; (o) 2-pyridyl;

(p) 4-pyridyl;

(q) 2-alkyl-5-pyridyl; and n is an integer from 1 to 10.

The term "aryl," as employed above and as used throughout theapplication and in the appended claims, is intended to be inclusive ofand should be understood as being inclusive of phenyl and substitutedphenyl, e.g., phenyl substituted with halogen(s) or alkyl group(s)having 1-4 carbon atoms. X can also be ##STR9## wherein R₂₈ is astraight chain or branched alkyl having 1 to 18 carbon atoms,cyclohexyl, benzyl, phenyl, t-butylphenyl or chlorophenyl.

When X is --SO₂ R₁, a preferred group of compounds is that in which R₁is a straight chain or branched alkyl having 1 to 18 carbon atoms,cyclopentyl, cyclohexyl, benzyl, phenyl, alkoxyphenyl having 1 to 3carbon atoms in the alkoxy group, phenoxyphenyl,bicyclo[2.2.1]heptylphenyl, halophenyl, piperidinoethylmethiodide, --R₂Sn(CH₃)₃ wherein R₂ is polymethylene having from 2 to 11 carbon atoms or--R₄ SO₂ R₅ Sn(CH₃)₃ wherein R₄ is ethylene and R₅ is as defined for R₂above.

These and other organotin compounds of this invention have been found toexhibit a wide variety of activities. For example, they have been founduseful as insecticides, acaricides and herbicides.

The compounds having these and related utilities are tetrasubstitutedtin compounds having the general formula ##STR10## wherein R' ishydrogen, hydroxyl, alkoxyl or a straight chain or branched alkyl grouphaving 1 to 5 carbon atoms;

X is (a) --SO₂ R₁, R' being hydrogen, and wherein R₁ is a straight chainor branched alkyl having 1 to 18 carbon atoms, cyclohexyl, benzyl,phenyl or phenyl substituted with one or more groups which may be thesame or different and which may be linear or branched alkyl having 1 to20 carbon atoms, cycloaliphatic having 4 to 6 carbon atoms, straightchain or branched alkenyl having 2 to 20 carbon atoms, alkoxy having 1to 8 carbon atoms, phenoxy, alkylthio having 1 to 8 carbon atoms,halogen, nitro, acetyl, acetamido, carboxyl, alkoxycarbonyl, carbamoyl,cyano, hydroxy, trifluoromethyl, benzyl, naphthyl or norbornyl;naphthyl, biphenylyl, piperidinoethylmethiodide, --R₂ Sn(CH₃)₃ whereinR₂ is polymethylene having from 2 to 11 carbon atoms, --R₄ SO₂ R₅Sn(CH₃)₃ wherein R₄ is ethylene and R₅ is as defined for R₂ above;

(b) --OR₇, wherein R₇ is a straight chain or branched alkyl having 1 to20 carbon atoms, haloalkyl, aryl, haloaryl, alkaryl, alkoxyaryl,epoxyalkylene wherein the alkylene group has 2 to 4 carbon atoms,N,N-dialkylaminoalkyl, tetrahydro-1,1-dioxo-3-thienyl, --R₈ Sn(CH₃)₃wherein R₈ is alkylene hving 2 to 11 carbon atoms, cycloaliphatic having4 to 6 carbon atoms or aryl;

(c) --SR₁₀, R' being hydrogen, and wherein R₁₀ is a straight chain orbranched alkyl having 1 to 18 carbon agtoms, cyclohexyl, benzyl, phenylor phenyl substituted with one or more groups which may be the same ordifferent and which may be linear or branched alkyl having 1 to 20carbon atoms, cycloaliphatic having 4 to 6 carbon atoms, straight chainor branched alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 8carbon atoms, alkylthio having 1 to 8 carbon atoms, halogen, nitro,acetyl, acetamido, carboxyl, alkoxycarbonyl, carbamoyl, cyano, hydroxy,trifluoromethyl, benzyl, naphthyl or norbornyl; naphthyl, biphenylyl,piperidinoethylmethiodide, --R₂ Sn(CH₃)₃ wherein R₂ is polymethylenehaving from 2 to 11 carbon atoms, --R₄ SO₂ R₅ Sn(CH₃)₃ wherein R₄ isethylene and R₅ is as defined for R₂ above;

(d) --COR₁₁, wherein R₁₁ is --NH₂, --NHNH₂, --NHCH₂ OH, --NHR₁₂ whereinR₁₂ is a straight chain or branched alkyl having 1 to 12 carbon atoms oraryl; --NHCH₂ NHCOR₂ SN(CH₃)₃, --OR₁₃ wherein R₁₃ is a straight chain orbranched alkyl having 1 to 15 carbon atoms, --(CH₂)_(m) OH wherein m isan integer from 2 to 4, --(CH₂)_(p) N(R₁₄)₂ wherein p is an integer from2 to 4 and R₁₄ is a straight chain or branched alkyl having 1 to 5carbon atoms, --(CH₂)_(q) OCOR₂ Sn(CH₃)₃ wherein q is as defined for pabove, --(CH₂)_(s) N.sup.⊕ (CH₃)₃ I.sup.⊖ wherein s is as defined for pabove;

(e) --NHCONH₂ ;

(f) --NHCSNH₂ ;

(g) 2-pyridyl;

(h) 4-pyridyl;

(i) 2-alkyl-5-pyridyl;

(j) 9-carbazolyl;

(k) 1 -imidazolyl;

(l) N-2-oxopyrrolidinyl;

(m) --OCOR₁₇, wherein R₁₇ is --NHR₁₈ wherein R₁₈ is a straight chain orbranched alkyl having 1 to 5 carbon atoms or aryl; 2-furyl; and--O(CH₂)_(t) Sn(CH₃)₃ wherein t is an integer from 2 to 11;

(n) --PO(OR₂₀)₂ wherein R₂₀ is a straight chain or branched alkyl having1 to 5 carbon atoms;

(o) tetrahydro-1,1-dioxo-2-thenyl;

(p) --Si(OR₂₁)₃ wherein R₂₁ is a straight chain or branched alkyl having1 to 5 carbon atoms; ##STR11## n is an integer from 1 to 10.

We recognize that the insecticidal, acaricidal and herbicidal activitiesof the compounds of the invention are derived from the trimethyltinsegment of the molecule, i.e., (CH₃)₃ Sn--. The degree and nature ofactivity of these compounds are also effected by that portion of themolecule that contains the ##STR12## radical as, for example,phytotoxicity to beneficial plants, herbicidal activity to noxiousplants, uptake and translocation in plants, retention in the soil, oraland/or dermal mammalian toxicity, control of physical properties such asvolatility and solubility, hydrolytic and/or oxidative stability,sensitivity to solar ultraviolet, ease of entry into the food chain,degradation by microorganisms and/or higher forms of life, and practicalformulation and useful application rate.

In general, the compounds of the invention can be obtained according tothe one-step reaction process described by R. Sommer and H. G. Kuivila,J. Org. Chem., 33, 802 (1968), which involves reacting a compoundcontaining an olefinic moiety with trimethyltin hydride according to thefollowing scheme: ##STR13## wherein X is as defined above, R' may behydrogen, a straight chain or branched alkyl group having 1 to 5 carbonatoms or an alkoxy group having 1 to 5 carbon atoms, and R" may behydrogen, hydroxyl, or an alkyl group having 1 to 5 carbon atoms, and mis an integer from 0 to 9.

In this synthesis, the substituted olefinic compounds and an equivalentamount of the organotin hydride are placed in a conventional glassreaction vessel under an inert atmosphere in the presence of a suitablesolvent, where desired or as required, and with adequate stirring. Thereaction mixture is irradiated by a mercury vapor lamp until no moreorganotin hydride is present, which is determined by infra-red spectrumanalysis noting the absence of additional Sn-H absorption. The time forthis to occur will vary depending upon the particular substitutedolefinic compound used but will generally be about 4 to 48 hours, but,when n is 3 or higher, can be as long as 232 hours. The reaction mixtureis normally maintained at a temperature of about 0° to 50° C. In caseswhere the reactants are heterogeneous and/or when the starting materialis a solid, ether solvents such as diethyl ether and tetrahydrofuran,aromatic solvents such as benzene and toluene, esters and nitriles suchas ethyl acetate and acetonitrile, alcohols such as methanol andethanol, amides such as dimethylformamide, and the like, may be used tofacilitate mixing of the reactants.

One mole of an unsaturated sulfone, formed by the addition of one moleof the organotin hydride to one mole of a sulfone containing twounsaturated (--C═C--) groups, for example a divinyl sulfone, may bereacted further according to (A) above with reagents such as mercaptans,amines, alcohols and phenols. The following equations in which thestarting sulfone is divinyl sulfone, as in Example 3 hereinbelow,illustrate this aspect of the invention: ##STR14## where Z may be (CH₃)₃Sn--, (R₂₄)₃ Si--, (R₂₅)₂ N--, R₂₆ S-- or a R₂₇ O-- group; R₂₄, R₂₅, R₂₆and R₂₇ may be a straight chain or branched alkyl group having 1 to 5carbon atoms, or an aryl group.

Employing the same general method described above for obtaining theorganotin compound of (A), two equivalents of the organotin hydride canbe reacted to form an adduct containing two organotin moieties accordingto the following equation: ##STR15## wherein R', R" and m are as definedas above. W may be a sulfonyl diradical (--SO₂ --) as in compounds 1 and2 in Table I hereinbelow, a 1,2-ethylenedisulfonyl diradical (--SO₂--CH₂ --CH₂ --SO₂ --) as in compound 17 in Table I hereinbelow, an oxydiradical (--O--) as in compounds 25 and 26 in Table I hereinbelow, athio diradical (--S--) as in compound 36 in Table I hereinbelow, anN,N'-methylenebiscarbamoyl diradical ##STR16## as in compound 41 inTable I hereinbelow, a 1,2-ethylenedioxydicarbonyl diradical ##STR17##as in compound 45 in Table I hereinbelow, a carbonyldioxy diradical##STR18## as in compound 52 in Table I hereinbelow, a phenylenediradical ##STR19## as in compound 60 in Table I hereinbelow, and a2,4,8,10-tetraoxospiro[5.5]undec-3,9-ylene diradical having thestructure: ##STR20## as in compound 63 in Table I hereinbelow. Thepreparative method is the same as that described for scheme (A) aboveexcept that two equivalents of the organotin hydride are required whenthe other reactant contains two olefinic moieties.

Where desired, purification of the organotin compounds can be achievedby using standard distillation, column chromatography, orrecrystallization techniques.

Alternatively, the compounds of this invention can be made by the methodof British Patent No. 966,813 to Karl Ziegler using conventional freeradical generators such as azobisisobutyronitrile, azotriphenylmethaneand the like.

Thus, a wide variety of substituted olefinic compound can be used toprepare the compounds of this invention. Examples of such compounds arelisted below and grouped according to their primary function. Inaddition, the compound numbers in which specific compounds from the listwere used to make the representative number of the compounds of thisinvention are also shown, these compounds being more fully identified inTable I hereinbelow.

    ______________________________________                                                                   Com-                                                                          pound                                                                         No.                                                ______________________________________                                        1.  Sulfones                                                                      divinyl sulfone              1, 2, 16                                         methyl vinyl sulfone;        3                                                ethyl vinyl sulfone;         4                                                n-propyl vinyl sulfone;                                                       isopropyl vinyl sulfone;     5                                                n-butyl vinyl sulfone;                                                        sec-butyl vinyl sulfone;     6                                                tert-butyl vinyl sulfone;                                                     n-pentyl vinyl sulfone;                                                       isopentyl vinyl sulfone;                                                      sec-pentyl vinyl sulfone;                                                     tert-pentyl vinyl sulfone;   7                                                n-hexyl vinyl sulfone;                                                        cyclohexyl vinyl sulfone;    11                                               4-methylcyclohexyl vinyl sulfone;                                             methallyl vinyl sulfone;                                                      n-octyl vinyl sulfone;       8                                                tert-octyl vinyl sulfone;                                                     benzyl vinyl sulfone;        12                                               4-chlorobenzyl vinyl sulfone;                                                 phenyl vinyl sulfone;        13                                               p-tolyl vinyl sulfone;       66                                               o-ethylphenyl vinyl sulfone;                                                  p-ethylphenyl vinyl sulfone; 67                                               p-n-propylphenyl vinyl sulfone;                                               p-i-propylphenyl vinyl sulfone;                                                                            68                                               p-n-butylphenyl vinyl sulfone;                                                p-s-butylphenyl vinyl sulfone;                                                p-t-butylphenyl vinyl sulfone;                                                                             14                                               p-i-butylphenyl vinyl sulfone;                                                p-n-amylphenyl vinyl sulfone;                                                                              69                                               p-t-amylphenyl vinyl sulfone;                                                                              70                                               p-n-hexylphenyl vinyl sulfone;                                                p-n-heptylphenyl vinyl sulfone;                                               p-n-heptylphenyl vinyl sulfone;                                               p-n-octylphenyl vinyl sulfone;                                                                             71                                               p-t-octylphenyl vinyl sulfone;                                                p-nonylphenyl vinyl sulfone;                                                  p-decylphenyl vinyl sulfone;                                                  p-dodecylphenyl vinyl sulfone;                                                                             72                                               p-n-dodecylphenyl vinyl sulfone;                                                                           73                                               p-tridecylphenyl vinyl sulfone;                                                                            74                                               p-cyclopentylphenyl vinyl sulfone;                                                                         79                                               p-cyclohexyl phenyl vinyl sulfone;                                                                         80                                               p-bicyclo[2.2.1]-hept-2-ylphenyl vinyl sulfone;                                                            81                                               3,4-dimethylphenyl vinyl sulfone;                                             2,4-dimethylphenyl vinyl sulfone;                                                                          75                                               2,5-dimethylphenyl vinyl sulfone;                                                                          76                                               2,4-diethylphenyl vinyl sulfone;                                                                           77                                               2,5-diethylphenyl vinyl sulfone;                                              2,4-diisopropylphenyl vinyl sulfone;                                          2,5-diisopropylphenyl vinyl sulfone;                                                                       78                                               2,5-di-t-butylphenyl vinyl sulfone;                                           2,5-dicyclohexylphenyl vinyl sulfone;                                         2,4,6-trimethylphenyl vinyl sulfone;                                          2,4,6-triethylphenyl vinyl sulfone;                                           2,4,6-triisopropylphenyl vinyl sulfone;                                       2,3,5,6-tetramethylphenyl vinyl sulfone;                                      2,3,4,5,6-pentamethylphenyl vinyl sulfone;                                    p-allylphenyl vinyl sulfone;                                                  p-propenylphenyl vinyl sulfone;                                               p-crotylphenyl vinyl sulfone;                                                 p-methallylphenyl vinyl sulfone;                                              p-4-pentenylphenyl vinyl sulfone;                                             p-3-methylcrotylphenyl vinyl sulfone;                                         p-oleylphenyl vinyl sulfone;                                                  p-methoxyphenyl vinyl sulfone;                                                                             82                                               p-ethoxyphenyl vinyl sulfone;                                                 p-butoxyphenyl vinyl sulfone;                                                 p-octoxyphenyl vinyl sulfone;                                                 2,4-dimethoxyphenyl vinyl sulfone;                                            2,5-dimethoxyphenyl vinyl sulfone;                                            3,4-dimethoxyphenyl vinyl sulfone;                                            p-methylthiophenyl vinyl sulfone;                                             p-butylthiophenyl vinyl sulfone;                                              p-octylthiophenyl vinyl sulfone;                                              5-chloro-2-methoxyphenyl vinyl sulfone;                                       2-chloro-4-methoxyphenyl vinyl sulfone;                                       3-chloro-4-methoxyphenyl vinyl sulfone;                                       5-bromo-2-methoxyphenyl vinyl sulfone;                                        2-bromo-4-methoxyphenyl vinyl sulfone;                                        3-bromo-4-methoxyphenyl vinyl sulfone;                                        3-acetamido-4-methoxyphenyl vinyl sulfone;                                    5-acetamido-2-methoxyphenyl vinyl sulfone;                                    5-nitro-2-methoxyphenyl vinyl sulfone;                                        5-nitro-2-methoxyphenyl vinyl sulfone;                                        2-nitro-4-methoxyphenyl vinyl sulfone;                                        3-nitro-4-methoxyphenyl vinyl sulfone;                                        2-methyl-4-methoxyphenyl vinyl sulfone;                                       2-methyl-5-methoxyphenyl vinyl sulfone;                                       2-methyl-5-chlorophenyl vinyl sulfone;                                        2-methyl-5-bromophenyl vinyl sulfone;                                         p-fluorophenyl vinyl sulfone;                                                                              84                                               p-bromophenyl vinyl sulfone; 83                                               p-chlorophenyl vinyl sulfone;                                                                              15                                               2,5-dichlorophenyl vinyl sulfone;                                             3,4-dichlorophenyl vinyl sulfone;                                                                          85                                               2,4,5-trichlorophenyl vinyl sulfone;                                          trifluoromethylphenyl vinyl sulfone;                                          4-chloro-3-nitrophenyl vinyl sulfone;                                         3-nitrophenyl vinyl sulfone;                                                  2-nitrophenyl vinyl sulfone;                                                  3,5-dichloro-2-hydroxyphenyl vinyl sulfone;                                   p-acetamidophenyl vinyl sulfone;                                              p-carboxyphenyl vinyl sulfone;                                                p-alkoxycarbonylphenyl vinyl sulfone;                                         p-carbamoylphenyl vinyl sulfone;                                              p-cyanophenyl vinyl sulfone;                                                  p-acetylphenyl vinyl sulfone;                                                 2-naphthyl vinyl sulfone;    86                                               4-biphenylyl vinyl sulfone;                                                   n-dodecyl vinyl sulfone;     9                                                n-octadecyl vinyl sulfone;   10                                               1,2-ethylenebis(vinyl sulfone);                                                                            17                                               1-ethyl-1,2-ethylenebis(vinyl sulfone);                                       1,4-tetramethylenebis(vinyl sulfone);                                         1,6-hexamethylenebis(vinyl sulfone);                                          1,8-octamethylenebis(vinyl sulfone);                                          2,2-propylidenebis(vinyl sulfone);                                            1,1'-methylenebismethyl vinyl sulfone;                                        2-(trimethylstannyl)ethyl vinyl sulfone;                                      methyl 3-butenyl sulfone;                                                     ethyl 4-pentenyl sulfone;                                                     n-propyl 5-hexenyl sulfone;                                                   isopropyl 6-heptenyl sulfone;                                                 n-butyl 7-octenyl sulfone;                                                    sec-butyl 8-nonenyl sulfone;                                                  tert-butyl 9-decenyl sulfone;                                                 n-pentyl 10-undecenyl sulfone;                                                isopentyl 3-butenyl sulfone;                                                  sec-pentyl 4-pentenyl sulfone;                                                tet-pentyl 5-hexenyl sulfone;                                                 n-hexyl 6-heptenyl sulfone;                                                   cyclohexyl 7-octenyl sulfone;                                                 4-methylcyclohexyl 8-nonenyl sulfone;                                         methallyl 9-decenyl sulfone;                                                  n-octyl 10-undecenyl sulfone;                                                 tert-octyl 3-butenyl sulfone;                                                 benzyl 4-pentenyl slfone;                                                     4-chlorobenzyl 5-hexenyl sulfone;                                             6-hexenyl phenyl sulfone;                                                     3-butenyl p-tolyl sulfone;                                                    3-butenyl p-t-butylphenyl sulfone;                                                                         87                                               4-pentenyl p-ethylphenyl sulfone;                                             5-hexenyl p-tolylphenyl slfone;                                                                            88                                               6-heptenyl p-n-propylphenyl slfone;                                           7-octenenyl p-i-propylphenyl sulfone;                                         8-nonenyl p-n-butylphenyl sulfone;                                            9-decenyl p-s-butylphenyl sulfone;                                            10-undecenyl p-tolyl sulfone;                                                                              89                                               4-pentenyl p-i-butylphenyl sulfone;                                           5-hexenyl p-n-amylphenyl sulfone;                                             6-heptenyl t-amylphenyl sulfone;                                              7-octenyl p-n-hexylphenyl sulfone;                                            8-nonenyl p-n-heptylphenyl sulfone;                                           9-decenyl p-octylphenyl sulfone;                                              1:-undecenyl t-octylphenyl sulfone;                                           3-butenyl p-nonylphenyl sulfone;                                              4-pentenyl p-decylphenyl sulfone;                                             5-hexenyl p-n-dodecylphenyl sulfone;                                          6-heptenyl p-dodecylphenyl sulfone;                                           7-octenyl p-tridecylphenyl sulfone;                                           8-nonenyl p-cyclopentylphenyl sulfone;                                        9-decenyl p-cyclohexylphenyl sulfone;                                         10-undecenyl bicyclo[2.2.1]hept-2-ylphenyl sulfone;                           3-butenyl 3,4-dimethylphenyl sulfone;                                         4-pentenyl 2,4-dimethylphenyl sulfone;                                        5-hexenyl 2,5-dimethylphenyl sulfone;                                         6-heptenyl 2,4-diethylphenyl sulfone;                                         7-octenyl 2,5-diethylphenyl sulfone;                                          8-nonenyl 2,4-diisopropylphenyl sulfone;                                      9-decenyl 2,5-diisopropylphenyl sulfone;                                      10-undecenyl 2,5-di-t-butylphenyl sulfone;                                    3-butenyl dicyclohexylphenyl sulfone;                                         4-pentenyl 2,4,6-trimethylphenyl sulfone;                                     5-hexenyl 2,4,6-triethylphenyl sulfone;                                       6-heptenyl 2,4,6-triisopropylphenyl sulfone;                                  7-octenyl 2,3,5,6-tetrmaethylphenyl sulfone;                                  8-nonenyl 2,3,4,5,6-pentamethylphenyl sulfone;                                9-decenyl p-methoxyphenyl sulfone;                                            1:-undecenyl p-ethoxyphenyl sulfone;                                          3-butenyl p-butoxyphenyl sulfone;                                             4-pentenyl p-octoxyphenyl sulfone;                                            5-hexenyl 2,4-dimethoxyphenyl sulfone;                                        6-heptenyl 2,5-dimethoxyphenyl sulfone;                                       7-octenyl 3,4-dimethoxyphenyl sulfone;                                        8-npnenyl p-methylthiophenyl sulfone;                                         9-decenyl p-butylthiophenyl sulfone;                                          10-undecenyl p-octylthiophenyl sulfone;                                       3-butenyl 5-chloro-2-methoxyphenyl sulfone;                                   4-pentenyl 2-chloro-4-methoxyphenyl sulfone;                                  5-hexenyl 3-chloro-4-methoxyphenyl sulfone;                                   5-hexenyl 3-chloro-4-methoxyphenyl sulfone;                                   6-heptenyl 5-bromo-2-methoxyphenyl sulfone;                                   7-octenyl 2-bromo-4-methoxyphenyl sulfone;                                    8-nonenyl 3-bromo-4-methoxyphenyl sulfone;                                    9-decenyl 3-acetamido-4-methoxyphenyl sulfone;                                10-undecenyl 5-acetamido-2-methoxyphenyl sulfone;                             3-butenyl 2-nitro-4-methoxyphenyl sulfone;                                    4-pentenyl 3-nitro-4-methoxyphenyl sulfone;                                   5-hexenyl 2-methyl-4-methoxyphenyl sulfone;                                   6-heptenyl 2-methyl-5-methoxyphenyl sulfone;                                  7-octenyl 2-methyl-5-chlorophenyl sulfone;                                    8-nonenyl 2-methyl-5-bromophenyl sulfone;                                     9-decenyl p-fluorophenyl sulfone;                                             10-undecenyl p-bromophenyl sulfone;                                           3-butenyl p-chlorophenyl sulfone;                                             4-pentenyl 2,5-dichlorophenyl sulfone;                                        5-hexenyl 3,4-dichlorophenyl sulfone;                                         6-heptenyl 2,4,5-trichlorophenyl sulfone;                                     7-octenyl rifluoromethylphenyl sulfone;                                       8-nonenyl 4-chloro-3-nitrophenyl sulfone;                                     9:deceny 3-nitrophenyl sulfone;                                               10-undecenyl 2-nitrophenyl sulfone;                                           3-butenyl 3,5-dichloro-2-hydroxyphenyl sulfone;                               4-pentenyl p-acetamidophenyl sulfone;                                         5-hexenyl p-carboxyphenyl sulfone;                                            6-heptenyl alkoxycarbonylphenyl sulfone;                                      7-octenyl carbamoylphenyl sulfone;                                            8-nonenyl cyanophenyl sulfone;                                                9-decenyl p-acetylphenyl sulfone;                                             10-undecenyl 2-napththyl sulfone;                                             3-butenyl 4-biphenylyl sulfone;                                               4-pentenyl n-dodecyl sulfone;                                                 5-hexenyl n-octadecyl sulfone.                                            2.  Ethers                                                                        divinyl ether;               25                                               ethyl vinyl ether;           18                                               n-propyl vinyl ether;                                                         isopropyl vinyl ether;                                                        n-butyl vinyl ether;         19                                               isobutyl vinyl ether;        20                                               n-pentyl vinyl ether;                                                         n-hexyl vinyl ethers;                                                         cyclohexyl vinyl ether;                                                       n-octyl vinyl ether;                                                          isooctyl vinyl ether;        21                                               n-decyl vinyl ether;         22                                               n-dodecyl vinyl ether;       23                                               hexadecyl vinyl ether;       33                                               venzyl vinyl ether;                                                           2,2,2-trifluoroethyl vinyl ether;                                                                          31                                               phenyl vinyl ethers;                                                          p-chlorophenyl vinyl ether;                                                   o-tolyl vinyl ether;                                                          p-methoxyphenyl vinyl ether;                                                  2,6,8-trimethyl-4-nonyl vinyl ethers;                                                                      65                                               N,N-dimethylaminoethyl vinyl ether;                                                                        32                                               diallyl ether;               26                                               allyl glycidyl ether;        24                                               allyl phenyl ether;          27                                               allyl p-tert-butylphenyl ether;                                                                            28                                               allyl p-methoxyphenyl ether; 29                                               allyl p-chlorophenyl ether;  30                                               allyl (tetrahydro-1,1-dioxo-3-thienyl)ether;                                                               34                                               1,4-divinyloxybutane;                                                         3-vinyl-7-oxabicyclo[4.1.0]heptane;                                           3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecene;                                                           63                                               3-butenyl vinyl ether;                                                        di(3-butenyl)ether;                                                           4-pentenyl ethyl ether;                                                       5-hexenyl n-propyl ether;                                                     6-heptenyl isopropyl ether;                                                   7-octenyl n-butyl ether;                                                      8-nonenyl isobutyl ether;                                                     9-decenyl n-pentyl ether;                                                     10-undecenyl n-hexyl ether;                                                   3-butenyl cyclohexyl ether;                                                   4-pentenyl n-octyl ether;                                                     5-hexenyl isooctyl ether;                                                     6-heptenyl n-nonyl ether;                                                     7-octenyl n-decyl ether;                                                      8-nonenyl n-dodecyl ether;                                                    9-decenyl hexadecyl ether;                                                    10-undecenyl benzyl ether;                                                    3-butenyl 2,2,2-trifluoroethyl ether;                                         4-pentenyl phenyl ether;                                                      5-hexenyl p-chlorophenyl ether;                                               6-heptenyl o-tolyl ether;                                                     7-octenyl p-methoxy ether;                                                    8-nonenyl 2,6,8-trimethyl-4-nonyl ether;                                      9-decenyl N,N-dimethylaminoethyl ether;                                       3-butenyl N,N-dimethylaminoethyl ether;                                       3-butenyl allyl ether;                                                        4-pentenyl glycidyl ether;                                                    5-hexenyl phenyl ether;                                                       6-heptenyl p-methylpenyl ether;                                               7-octenyl p-t-butylphenyl ether;                                              8-nonenyl p-methoxyphenyl ether;                                              9-decenyl p-chlorophenyl ether;                                               10-undecenyl p-bromophenyl ether;                                             3-butenyl p-trifluoromethylphenyl ether;                                      4-pentenyl p-methoxyphenyl ether;                                             5-hexenyl(tetrahydro-1,1-dioxo-3-thienyl) ether.                          3.  Thioethers                                                                    diallyl sulfide;             36                                               allyl methyl sulfide;                                                         allyl ethyl sulfide;                                                          allyl n-propyl sulfide;                                                       allyl isopropyl sulfide;                                                      allyl n-butyl sulfide;                                                        allyl isobutyl sulfide;                                                       allyl n-pentyl sulfide;                                                       allyl n-hexyl sulfide;                                                        allyl cyclohexyl sulfide;                                                     allyl n-octyl sulfide;                                                        allyl isooctyl sulfide;                                                       allyl decyl sulfide;                                                          allyl hexadecyl sulfide;                                                      allyl benzyl sulfide;                                                         allyl phenyl sulfide;        35                                               allyl p-chlorophenyl sulfide;                                                 methyl vinyl sulfide;                                                         ethyl vinyl sulfide;                                                          n-propyl vinyl sulfide;                                                       n-butyl vinyl sulfide;                                                        n-hexyl vinyl sulfide;                                                        cyclohexyl vinyl sulfide;                                                     n-octyl vinyl sulfide;                                                        hexadecyl vinyl sulfide;                                                      allyl vinyl sulfide;                                                          benzyl vinyl sulfide;                                                         pheny vinyl sulfide;                                                          p-tert-butylphenyl vinyl sulfide;                                             o-toly vinyl sulfide;                                                         p-chlorophenyl vinyl sulfide;                                                                              37                                               3-butenyl methyl sulfide;                                                     4-pentenyl ethyl sulfide;                                                     5-hexenyl n-propyl sulfide;                                                   6-heptenyl isopropyl sulfide;                                                 7-octenyl n-butyl sulfide;                                                    8-nonenyl isobutyl sulfide;                                                   9-decenyl n-pentyl sulfide;                                                   10-undecenyl n-hexyl sulfide;                                                 3-butenyl cyclohexyl sulfide;                                                 4-pentenyl n-octyl sulfide;                                                   5-hexenyl isooctyl sulfide;                                                   6-heptenyl decyl sulfide;                                                     7-octenyl hexadecyl sulfide;                                                  8-nonenyl benzyl sulfide;                                                     9-decenyl phenyl sulfide;                                                     10-undecenyl p-chlorophenyl sulfide;                                          3-butenyl benzyl sulfide;                                                     4-pentenyl p-tert-butylphenyl sulfide;                                        5-hexenyl o-tolyl sulfide;                                                    6-heptenyl p-bromophenyl sulfide;                                             di(3-butenyl)sulfide.                                                     4.  Esters                                                                        divinyl carbonate;                                                            diallyl carboate;            52                                               dimethallyl carbonnate;                                                       allyl N-methyl carbamate;    54                                               allyl N-ethyl carbamate;                                                      allyl N-propyl carbamate;                                                     allyl N-n-butyl carbamate;                                                    allyl N-n-octyl carbamate;                                                    allyl N-dodecyl carbamate;                                                    allyl N-phenyl carbamate                                                      allyl 2-furoate;             53                                               methyl acrylate;                                                              ethyl acrylate;              42, 43                                           n-propyl acrylate;                                                            isopropyl acrylate;                                                           n-butyl acrylate;                                                             n-pentyl acrylate;                                                            n-hexyl acrylate;                                                             cyclohexyl acrylate;                                                          n-octyl acrylate;                                                             n-decyl acrylate;                                                             n-dodecyl acrylate;          44                                               n-octadecyl acrylate;                                                         benzyl acrylate;                                                              phenyl acrylate;                                                              p-chlorophenyl acrylate;                                                      1,2-ethylene diacrylate;     45                                               1,4-tetramethylene diacrylate;                                                1,6-hexamethylene diacrylate;                                                 1,8-octamethylene diacrylate;                                                 1,10-decamethylene diacrylate;                                                1,12-dodecamethylene diacrylate;                                              methyl methacrylate;                                                          ethyl methacrylate;                                                           propyl methacrylate;                                                          isopropyl methacrylate;                                                       n-butyl methacrylate;                                                         hexyl methacrylate;                                                           cyclohexyl methacrylate;                                                      n-octyl methacrylate;                                                         n-decyl methacrylate;                                                         n-dodecyl methacrylate;                                                       2-hydroxyethyl methacrylate;                                                  benzyl methacrylate;                                                          allyl methacrylate;                                                           phenyl methacrylate;                                                          p-chlorophenyl methacrylate;                                                  tert-butylaminoethyl methacrylate;                                            N-N-dimethylaminoethyl methacrylate;                                          1,2-ethylene dimethacrylate;                                                  1,4-tetramethylene dimethacrylate;                                            1,6-hexamethylene dimethacrylate;                                             3-butenyl vinyl carbonate;                                                    4-pentenyl allyl carbonate;                                                   5-hexenyl methallyl carbonate                                                 6-heptenyl N-methyl carbamate;                                                7-octenyl N-ethyl carbamate;                                                  8-nonenyl N-propyl carbamate;                                                 9-decenyl N-n-butyl carbamate;                                                10-undecenyl N-n-octyl carbamate;                                             3-butenyl N-dodecylcarbamate;                                                 4-pentenyl N-phenyl carbamate;                                                5-hexenyl 2-furoate;                                                          methyl 6-heptenoate;                                                          ethyl 7-octenoate;                                                            n-propyl 8-nonenoate;                                                         isopropyl 9-decenoate;                                                        n-butyl 10-undecenoate;                                                       n-pentyl 3-butenoate;                                                         n-hexyl 4-pentenoate;                                                         cyclohexyl 5-hexenoate;                                                       n-decyl 7-octenoate;                                                          n-dodecyl 8-nonenoate;                                                        n-octadecyl 9-decenoate;                                                      benzyl 10-undecenoate;                                                        phenyl 3-butenoate;                                                           p-chlorophenyl 4-pentenoate;                                                  1,2-ethylene di(4-pentenoate);                                                1,4-tetramethylene di(5-hexenoate);                                           1,6-hexamethylene di(6-heptenoate);                                           1,8-octamethylene di(7-octenoate);                                            1,1:-decamethylene di(8-nonenoate);                                           1,12-dodecamethylene di(9-deceneoate);                                        ethyl 1-methyl-3-butenoate;                                                   propyl 2-methyl-4-pentenoate;                                                 isopropyl 2-methyl-5-hexenoate;                                               n-butyl 2-methyl-6-heptenoate;                                                hexyl 2-methyl-7-octenoate;                                                   cyclohexyl 2-methyl-8-nonenoate;                                              n-octyl 2-methyl-9-decenoate;                                                 n-decyl 2-methyl-10-undecenoate;                                              n-dodecyl 2-methyl-3-butenoate;                                               2-hydroxyethyl 2-methyl-4-pentenoate;                                         benzyl 2-methyl-5-hexenoate;                                                  allyl 2-methyl-6-heptenoate;                                                  phenyl 2-methyl-7-octenoate;                                                  p-chlorophenyl 2-methyl-8-nonenoate;                                          tet-butylaminoethyl 2-methyl-9-decenoate;                                     N,N-dimethylaminoethyl 2-methyl-10-undecenoate;                               1,2-ethylene di(2-methyl-3-butenoate);                                        1,4-tetramethylene di(2-methyl-4-pentenoate);                                 1,6-hexamethylene di(2-methyl-5-hexenoate).                               5.  Amides                                                                        acrylamide;                  38                                               N-methylacrylamide;                                                           N-hydroxymethylacrylamide;   40                                               N-ethylacrylamide;                                                            N-isopropylacrylamide;                                                        N-n-butylacrylamide;                                                          N-tetr-butylacrylamide;      39                                               N-n-octylacrylamide;                                                          N-dodecylacrylamide;                                                          N,N'-methylenebisacrylamide; 41                                               N-phenylacrylamide;                                                           N,N'-tetramethylenebisacrylamide;                                             N,N'-hexamethylenebisacrylamide;                                              N-allylacrylamide;                                                            methacrylamide;                                                               N-methylmethacrylamide;                                                       N-ethylmethacrylamide;                                                        N-isopropylmethacrylamide;                                                    N-n-butylmethacrylamide;                                                      N-hexadecylmethacrylamide;                                                    N-tert-butylmethacrylamide;                                                   N-octadecylmethacrylamide;                                                    N-phenylmethacrylamide;                                                       N,N-dimethylmethacrylamide;                                                   N,N-diethylmethacrylamide;                                                    N,N-di-n-butylmethacrylamide;                                                 N,N-di-n-octylmethacrylamide;                                                 N-methyl-3-butenamide;                                                        N-hydroxy-4-pentenamide;                                                      N-ethyl-5-hexenamide                                                          N-isopropyl-6-heptenamide;                                                    N-n-butyl-7-octenamide;                                                       N-tert-butyl-8-nonenamide;                                                    N-n-octyl-9-decenamide;                                                       N-dodecyl-10-undecenamide;                                                    N-phenyl-3-butenamide;                                                        N,N'-methylenebis(4-pentenamide);                                             N-phenyl-5-hexenamide;                                                        N,N'-tetramethylenebis(6-heptenamide);                                        N,N'-hexamethylenebis(7-octenamide);                                          N-allyl-8-nonenamide;                                                         N-methyl-9-decenamide;                                                        N-methyl-2-methyl-10-undecenamide;                                            N-ethyl-2-methyl-3-butenamide;                                                N-isopropyl-2-methyl-4-pentenamide;                                           N-n-butyl-2-methyl-5-hexenamide;                                              N-hexadecyl-2-methyl-6-heptenamide;                                           N-tert-butyl-2-methyl-7-octenamide;                                           N-octadecyl-2-methyl-8-nonenamide;                                            N-phenyl-2-methyl-9-decenamide;                                               N-phenyl-2-methyl-10-undecenamide;                                            N-phenyl-2-methyl-3-butenamide;                                               N,N-dimethyl-2-methyl-4-pentenamide;                                          N,N-diethyl-2-methyl-5-hexenamide;                                            N,N-di-n-butyl-2-methyl-6-heptenamide;                                        N,N-di-n-octyl-2-methyl-7-octenamide.                                     6.  Phosphonates                                                                  diethyol vinylphosphonate;   51                                               di-n-butyl vinylphosphonate;                                                  di-n:hexyl vinylphosphonate;                                                  dicyclohexyl vinyl phosphonate;                                               di-n-octyl vinylphosphonate;                                                  di-dodecyl vinylphosphonate;                                                  di-hexadecyl vinylphosphonate;                                                dibenzyl vinylphosphonate;                                                    diphenyl vinylphosphonate;                                                    diethyl 1-ethoxyvinylphosphonate.                                                                          64                                           7.  Pyridines                                                                     2-vinylpyridine;             55                                               3-vinylpyridine;                                                              4-vinylpyridine;             57                                               2-methyl-5-vinylpyridine;    56                                               5-methyl-2-vinylpyridine;                                                     6-methyl-2-vinylpyridine;                                                     6-butyl-2-vinylpyridine;                                                      2,6-dimethyl-4-vinylpyridine;                                                 4-t-butyl-2-vinylpyridine;                                                    2-allylpyridine;                                                              3-allylpyridine;                                                              4-allylpyridine;                                                              2-(3-butenyl)pyridine;                                                        3-(3-butenyl)pyridine;                                                        4-(3-butenyl)pyridine;                                                        3-(4-pentenyl)pyridine;                                                       4-(5-hexenyl)pyridine;                                                        2-methyl-5(3-butenyl)pyridie;                                                 2-methyl-5(7-heptenyl)pyridine;                                               2-methyl-5(9-nonenyl)pyridine;                                                5-methyl-2(4-pentenyl)pyridine;                                               5-methyl-2(8-octenyl)pyridine;                                                5-methyl-2-(8-octenyl)pyridine;                                               5-methyl-2(10-decenyl)pyridine;                                               6-methyl-2-(3-butenyl)pyridine;                                               6-butyl-2-(4-penytenyl)pyridine;                                              2,6-dimethyl-2-(3-butenyl)pyridine;                                           2,6-dimethyl-2-(5-hexenyl)pyridine;                                           4-t-butyl-2-(6-heptenyl)pyridine.                                         8.  Other Nitrogen Heterocycles                                                   N-vinyl imidazole;           50                                               N-vinyl-2-methyl imidazole;                                                   N-vinyl-2-phenyl imidazole;                                                   N-vinyl-4,5-dimethyl imidazle;                                                N-vinyl-4,5-diphenyl imidazle;                                                N-vinyl carbazole;           48                                               N-vinyl-2-pyrrolidinone;     49                                               N-(3-butenyl)imidazole;                                                       N(5-hexenyl)imidazole;                                                        N-(6:heptenyl)-2-methyl imidazole;                                            N-(7-octenyl)-2-phenyl imidazle;                                              N-(-nonenyl)-4,5-dimethyl imidazole;                                          N-(8-decenyl)-4,5-diphenyl imidazole;                                         N-(9-decenyl)-4,5-diphenyl imidazole;                                         N-(10-undecenyl)carbazole;                                                    N-(3-butenyl)-2-pyrrolidinone;                                                N-(5-hexenyl)-2-pyrrolidinone;                                                N-(7-octenyl)-2-pyrrolidinone.                                            9.  Ureas                                                                         allyl urea;                  46                                               N-allyl-N'-phenyl urea;                                                       N-allyl-N'-benzoyl urea;                                                      N-allyl-N'-butyl urea;                                                        N-allyl-N'-methyl urea;                                                       N-allyl-N'-n-octyl urea;                                                      N,N'-diallyl urea;                                                            N-allyl-N',N'-dimethyl urea;                                                  N-allyl-N',N'-dibutyl urea;                                                   N-allyl-N',N'-diphenyl urea;                                                  N-(3-butenyl)urea;                                                            N-(4-pentenyl)-N'-phenyl urea;                                                N-(5-hexenyl)-N'-benzoyl urea;                                                N-(6-heptenyl)-N'-butyl urea;                                                 N-(7-octenyl)-N'-methyl urea;                                                 N-(8-nonenyl)-N'-n-octyl urea;                                                N,N'-di(9-decenyl)urea;                                                       N-(10-undecenyl)-N',N'-dimethyl urea;                                         N-(3-butenyl)-N',N'-dibutyl urea;                                             N-(4-pentenyl)-N',N'-diphenyl urea.                                       10. Thioureas                                                                     allyl thiourea;              47                                               N-allyl-N'-benzoyl thiourea;                                                  N-allyl-N'-butyl thiourea;                                                    N-allyl-N'-methyl thiourea;                                                   N-allyl-N'-n-octyl thiourea;                                                  N-allyl-N'-phenyl thiourea;                                                   N,N'-diallyl thiourea;                                                        N-allyl-N',N'-dimethyl thiourea;                                              N-allyl-N',N'-dibutyl thiourea;                                               N-allyl-N',N'-diphenyl thiourea;                                              N-(3-butenyl)thiourea;                                                        N-(4-pentenyl)-N'-benzoyl thiourea;                                           N-(5-hexenyl)-N'-butyl thiourea;                                              N-(6-heptenyl)-N'-methyl thiourea;                                            N-(7-octenyl)-N'-n-octyl thiourea;                                            N-(8-nonenyl)-N'-phenyl thiourea;                                             N,N'-di(9-decenyl)thiourea;                                                   N-(10-undecenyl)-N',N'-dimethyl thiourea;                                     N-(3-butenyl)-N',N'-dibutyl thiourea;                                         N-(4-pentenyl)-N',N'-diphenyl thiourea;                                   11. Silanes                                                                       vinyltrimethoxysilane;                                                        vinyltriethoxysilane;        59                                               vinyltributoxysilane;                                                         vinyltrihexyloxysilane;                                                       vinyltricyclohexyloxysilane;                                                  vinyltrioctoxysilane;                                                         vinyltriphenoxysilane;                                                        vinyltribenzyloxysilane;                                                      divinyldimethylsilane;                                                        allyltrimethoxysilane;                                                        allyltriethoxysilane;                                                         allyltributoxysilane;                                                         allyltricyclohexyloxysilane;                                                  allyltriphenoxysilane;                                                        (3-butenyl)trimethoxysilane;                                                  (4-pentenyl)triethoxysilane;                                                  (5-hexenyl)tributoxysilane;                                                   (6-heptenyl)trihexyloxysilane;                                                (7-octenyl)tricyclohexyloxysilane;                                            (8-nonenyl)trioctoxysilane;                                                   (9-decenyl)triphenoxysilane;                                                  (10-undecenyl)tribenzyloxysilane;                                             (3-butenyl)tribenzyloxysilane;                                                (4-pentenyl)triphenoxysilane;                                                 (5-hexenyl)trioctoxysilane;                                                   (6-heptenyl)tricyclohexyloxysilane;                                           (7-octenyl)trihexyloxysilane.                                             12. Alcohols                                                                      allyl alcohol;               62                                               methallyl alcohol;                                                            3-buten-1-ol;                                                                 2-methyl-2-propen-1-ol;                                                       4-penten-1-ol;                                                                4-penten-2-ol;                                                                1-penten-3-ol;                                                                2-methyl-3-buten-1-ol;                                                        3-methyl-3-buten-1-ol;                                                        2-methyl-4-penten-2-ol;                                                       4-methyl-1-penten-3-ol;                                                       1,5-hexadien-3-ol;                                                            9-decen-1-ol;                                                                 10-undecen-1-ol;                                                              1-(tetrahydro-1,1-dioxo-2-thienyl)-3-buten-2-ol;                                                           58                                               5-hexen-1-ol;                                                                 6-hepten-1-ol;                                                                7-octen-1-ol;                                                                 8-nonen-1-ol.                                                             13. Nitriles                                                                      acrylonitrile;               61                                               methacrylonitrile;                                                            allyl cyanide;                                                                3-buteneitrile;                                                               4-pentenenitrile;                                                             5-hexenenitrile;                                                              6-heptenenitrile;                                                             7-octenenitrile;                                                              8-nonenenitrile;                                                              9-decenenitrile;                                                              10-undecenenitrile.                                                       14. Benzenes                                                                      o-divinylbenzene;                                                             m-divinylbenzen;                                                              p-divinylbenzene;                                                             m-diisopropenylbenzene;      60                                               p-diisopropenylbenzene;                                                       allyl (3,4-methylenedioxy)benzene;                                            2-chlorostyrene;                                                              3-chlorostyrene;                                                              4-chlorostyrene;                                                              4-methylstyrene;                                                              o-methylstyrene;                                                              4-methoxystyrene;                                                             4:ethoxystyrene;                                                              2,5-dimethoxystyrene;                                                         2,5-dichlorostyrene;                                                          (3-butenyl)benzene;                                                           (4-pentenyl)benzene;                                                          p-di(5-hexenyl)benzene;                                                       m-di(6-heptenyl)benzene;                                                      p-di(6-heptenyl)benzene;                                                      7-octenyl-(3,4-methylenedioxy)benzene;                                        2-chloro-(7-octenyl)benzene;                                                  3-bromo-(8-nonenyl)benzene;                                                   4-chloro-(9-decenyl)benzene;                                                  4-methyl-(10-undecenyl)benzene;                                               2-methyl-(3-butenyl)benzene;                                                  4-methoxy-(4-pentenyl)benzene;                                                4-ethoxy-(5-hexenyl)benzene;                                                  2,5-dimethoxy-(6-heptenyl)benzene;                                            2,5-dichloro-(7-octenyl)benzene;                                              2-trifluoromethyl-(8-nonenyl)benzene;                                         2,5-dibromo-(9-decenyl)benzene.                                           ______________________________________                                    

Trimethyl tin hydride having the following formula is used in thisinvention: (CH₃)₃ Sn-H. This organotin hydride is prepared by knownprocedures such as are described in the following references:

K. hayashi, J. Iyoda and I. Shiihara, J. Organometal. Chem., 10, 81(1967).

H. g. kuivila, Advan. Organometal Chem., 1, 47 (1964).

W. p. neumann, Angew. Chem., Internat. Edit., 2, 165 (1963).

Application of the compounds of the invention as insecticides andherbicides can be carried out in a number of ways. For practicalapplications, the compounds of the invention can be used alone, ordissolved or suspended in suitable carriers such as water, alcohols,ketones, phenols, toluene or xylenes. Optionally, one or more surfaceactive agents and/or inert diluents can be added to the formulation tofacilitate handling. The formulations can take the form of dusts,granules, wettable powders, pastes, emulsifiable concentrates, aerosols,water solution concentrates, or a water soluble solid.

For example, the compounds of the invention can be applied as dusts whenadmixed with or absorbed on powdered solid carriers, such as the variousmineral silicates, e.g., mica, talc, pyrophillite and clays, or asliquids or sprays when in a liquid carrier, as in solution in a suitablesolvent such as acetone, benzene or kerosene, or dispersed in a suitablenon-solvent medium, for example, water. In protecting plants (the termincluding plant parts), the chemicals of the present invention arepreferably applied as aqueous emulsions containing a surface-activedispersing agent which may be an anionic, nonionic or cationicsurface-active agent. Such surface-active agents are well known andreference is made to U.S. Pat. No. 2,547,724, columns 3 and 4, fordetailed examples of the same. The chemicals of the invention may bemixed with such surface-active dispersing agents, with or without anorganic solvent, as concentrates for subsequent addition of water tomake aqueous suspensions of the chemicals of the desired concentration.The chemicals of the invention may be admixed with powdered solidcarriers, such as mineral silicates together with a surface-activedispersing agent so that a wettable powder is obtained which may then beapplied directly to loci to be protected, or may be shaken with water toform a suspension of the chemical (and powdered solid carrier) in waterfor application in that form. The chemicals of the present invention maybe applied to loci to be protected by the aerosol method. Solutions foraerosol treatment may be prepared by dissolving the chemical directly inthe aerosol carrier which is liquid under pressure but which is a gas atordinary temperature (e.g., 20° C.) and atmospheric pressure, or theaerosol solution may be prepared by first dissolving the chemical inless volatile solvent and then admixing such solution with the highlyvolatile liquid aerosol carrier. The chemicals may be used admixed withcarriers that are active themselves, for example, other insecticides,acaricides, fungicides or bactericides.

These formulations will contain amounts of the compounds effective forthe particular method of control. These amounts can vary widely;typically, the range is from 0.1 to 95% active ingredient. Spraydilutions can contain from a few parts per million to full strengthconcentrates applied by ultra low volume techniques. Concentration perunit area, where plants are the area treated, can vary from 0.01 to 10pounds per acre.

Commonly, the compounds are applied directly. To control aphids, forexample, sprays of the compounds are applied to the aphids directly, toplants upon which they feed, or both. Sprays applied to theaphid-infested plants kill effectively even if direct contact does notoccur, as where the aphids cling to the inner surface of a curled upleaf or lie in a protected leaf sheath of, for example, a grain plant.Another effective method of attack involves application of the compoundsto the soil or other medium in which insect-infested plants live. Thecompounds act systemically upon the insects after the compound isabsorbed by the plants.

Harmful insects and related pests, such as mites, attack a wide varietyof plants, including both ornamental and agricultural plants such aschrysanthemum, azalea, cotton, corn, wheat, apple and tobacco, andinflict damage by withdrawing vital juices from the plants, by secretingtoxins and often by transmitting diseases. The compounds of theinvention can prevent such damage. The methods of application, and theselection and concentration of these compounds will, of course, varydepending upon such circumstances as area, climate, prevalent diseases,etc. One skilled in the art can select the proper approach by simpleexperiments.

The following examples demonstrate the use of the above describedprocedures in obtaining the organotin compounds of this invention andtheir utilization as insecticides and herbicides:

EXAMPLE 1

An 80-ml, two-necked, pyrex glass Schlenk reaction tube fitted with amagnetic stirrer was swept thoroughly with nitrogen and maintained in anair-free condition. The tube was then charged with a mixture of 16.5 g(100 mmoles) of trimethyltin hydride and 5.9 g (50 mmoles) of divinylsulfone, stoppered and then irradiated by means of a 100 watt mercuryvapor lamp for 4 hours. The reaction mixture was maintained at 20° C.and stirred magnetically. Recrystallization of the solid product frompetroleum ether gave 15 g of 2,2'-sulfonylbisethyltrimethylstannane,m.p. 78.5°-80.5° C., compound 1 of Table I. The presence of both thesulfonyl and trimethyltin groups was indicated by the strong infraredabsorption bands at 1300 cm⁻¹, 1240 cm⁻¹, 1140 cm⁻¹, 1105 cm⁻¹ and 765cm⁻¹ using a KBr disc. Nuclear magnetic resonance spectroscopy (NMR)showed the following: the protons alpha to the sulfonyl moiety appearedas a complex multiplet centered at 302 Hz (4 protons), the protons betato the sulfonyl moiety appeared as a complex multiplet centered at114.5Hz (4 protons), the protons of the trimethyltin group appeared at14.5 Hz, singlet accompanied by one satellite band on either side (9protons).

Analysis: Calc'd for C₁₀ H₂₆ O₂ SSn (percent): C, 26.9; H, 5.87; S,7.17; Sn, 53.0. Found: C, 26.9; H, 6.16; S, 6.89; Sn, 52.6.

EXAMPLE 2

This example illustrates the use of a solvent in the reaction describedin Example 1.

Using the apparatus and method of Example 1, trimethyltin hydride (46 g,279 mmoles), divinyl sulfone (16.5 g, 139 mmoles), and 30 ml of benzenewere charged into the glass Schlenk reaction tube. The tube wasirradiated with stirring at 20° C. under a blanket of nitrogen for 18hours. After filtration and evaporation of the solvent, the crudeproduct was recrystallized from petroleum ether to give 48.5 g, m.p.78.3°-79.3°, of 2,2'-sulfonylbisethyltrimethylstannane, compound 2 ofTable I. Analysis was the same as in Example 1 above.

Compounds 16, 46 and 53, which are shown in Table I hereinbelow, wererespectively prepared using the apparatus of Example 1 and the followingspecific procedures:

EXAMPLE 3

A mixture of 4.4 ml (5 g, 42.4 mmoles) of divinyl sulfone, 5 ml (42.4mmoles) of trimethyltin hydride and 5 ml of toluene was irradiated for18 hours. A liquid residue was obtained after filtration and evaporationof solvent. Five milliliters of piperidine was added to the crudeproduct with stirring and cooling. After stirring for 2 hours at roomtemperature, the excess piperidine was removed under reduced pressureleaving 9.2 g of an oil. To a solution of 5.2 g of this oil in 50 ml ofbenzene was added 1.25 ml of methyl iodide. After stirring for 3 days atroom temperature, 2.3 g of a solid was collected by filtration.Purification of the solid by precipitation from an acetone solution withethyl ether gave 2-(2-piperidinoethylsulfonyl)-ethyltrimethylstannane,methiodide, m.p. 122°-124° C., compound 16 of Table I. The presence ofboth the sulfonyl and trimethyltin moieties was indicated by theinfrared absorption bands at 1305 cm³¹ 1, 1260 cm⁻¹ and 1120 cm⁻¹ and at770 cm⁻¹, using a KBr disc.

Analysis: Calc'd for C₁₃ H₃₀ INO₂ SSn (percent): C, 30.61; H, 5.93; N,2.75. Found: C, 30.08; H, 5.87; N, 2.83.

EXAMPLE 4

A mixture of 8 g (30 mmoles) of 2-(ethoxycarbonyl)ethyltrimethylstannane(compound 47), 5 ml of 95% hydrazine (150 mmoles) in 10 ml of ethanolwas refuxed for 2 hours. The volatiles were removed at reduced pressure.Distillation of the crude product afforded 5.26 g of2-(hydrazinocarbonyl)ethyltrimethylstannane, b.p. 92°-98° C. (0.07 mm),compound 42 of Table I. The infrared spectrum of the distillate showedthe following characteristic absorptions: 3300 cm⁻¹ (N-H), 1660 cm⁻¹ and1530 cm⁻¹ ##STR21## and 760 cm⁻¹ (--Sn(CH₃)₃). A gas chromatogram of thesample showed a single peak on a 6 feet × 1/8 inch commercially obtainedcolumn packed with 10% of silicone gum rubber on silanized diatomaceousearth. The NMR spectrum exhibited the following proton absorptions: abroad singlet at 752 Hz (1 proton) assigned to N-H, a singlet at 388 Hz(2 protons) assigned to NH₂, a triplet centered at 235 Hz (2 protons)assigned to ##STR22## a triplet centered at 98 Hz (2 protons) assignedto CH₂ -Sn, and a singlet centered at 6 Hz (9 protons) assigned toSn(CH₃)₃.

Analysis: Calc'd for C₆ H₁₆ N₂ OSn (percent): C, 28.72; H, 6.43; N,11.17. Found: C, 28.08; H, 6.44; N, 10.53.

EXAMPLE 5

An 80 ml, two-necked, pyrex glass Schlenk reaction tube containing aTeflon coated magnetic stir bar was swept thoroughly with nitrogen andmaintained in an air-free condition. The tube was charged with 10.7 g(42.5 mmoles) of 3-butenyl-4-t-butylphenyl sulfone and 7.0 g (42.5mmoles) of trimethyltin hydride, stoppered, and placed in a 20° C. waterbath. The tube was irradiated for 70 hours by a 100 watt mercury vaporlamp which was situated in a large test tube and placed in the same bath5-10 cm. from the reaction tube. Recrystallization of the solid productfrom petroleum ether afforded 3.6 g of4-(4-t-butylphenylsulfonyl)butyltrimethylstannane, m.p. 80°-81.8° C. Thepresence of both the sulfonyl and trimethyltin moieties was indicated bystrong infrared absorption bands at 1300 cm⁻¹, 1282 cm⁻¹, 1147 cm⁻¹(--SO₂ --) and 780 cm⁻¹ [(CH₃)₃ Sn--] employing a KBR disc. Nuclearmagnetic resonance spectroscopy (NMR) showed the following:

The aromatic protons appeared as two multiplets each centered at 777 and753 Hz (each having 2 protons); the protons alpha to the sulfonyl moietyappeared as a complex multiplet centered at 307 Hz (2 protons); themethylene protons beta and gamma to the sulfone group appeared as acomplex multiplet centered at 162 Hz (4 protons); the methyl protons ofthe t-butyl group appeared as a singlet at 134 Hz (9 protons); themethylene protons adjacent to the tin atom appeared as a complex moietycentered at 73 Hz (2 protons); the protons of the trimethyltin groupappeared at the same chemical shift as tetramethylsilane (the internalstandard) ≈ 1 Hz.

Analysis: Calc'd for C₁₇ H₃₀ O₂ SSn (percent): C, 48.94; H, 7.25; S,7.68; Sn, 28.45. Found: C, 49.06; H, 7.33; S, 8.19; Sn, 27.60.

EXAMPLE 6

The procedure described in Example 5 was employed except that 10.1 g(42.5 mmoles) of 5-hexenyl p-tolyl sulfone and 14.0 g (85 mmoles) oftrimethyltin hydride were the reactants. The reaction mixture wasirradiated for 232 hours. The excess trimethyltin hydride was allowed toevaporate from the reaction mixture under a flow of nitrogen. Theunreacted 5-hexenyl p-tolyl sulfone was removed from the reactionmixture by distillation at 1 × 10⁻³ mm Hg leaving 3.25 g of crudeproduct. Column chromatography of the distillation residue over silicagel, employing toluene and 1% acetone in toluene as eluents, afforded anoil, 6-(p-tolylsulfonyl)hexyltrimethylstannane. The presence of both thesulfonyl and trimethyltin moieties was indicated by the strong infraredabsorption bands at 1315 cm⁻¹, 1300 cm⁻¹, 1285 cm⁻¹ and 1140 cm⁻¹ (--SO₂--) and 760 cm⁻¹ [(CH₃)₃ Sn--]. NMR showed the following:

The aromatic protons appeared as two multiplets each centered at 775 and732 Hz (2 protons each); the protons alpha to the sulfonyl groupappeared as a complex multiplet centered at 303 Hz (2 protons); themethyl protons of the tolyl group appeared as a singlet at 243 Hz (3protons); the methylene protons beta through epsilon to the sulfonegroup appeared as a broadened complex multiplet centered at 147 Hz (8protons); the protons of the methylene group attached to the tin atomappeared as a triplet centered at 74 Hz (protons); the protons of thetrimethyltin group appeared as a singlet at -2 Hz accompanied by onesatellite band on either side (9 protons).

Analysis: Calc'd for C₁₆ H₂₈ O₂ SSn (percent): C, 47.67; H, 7.00. Found:C, 47.52; H, 7,07.

EXAMPLE 7

The procedure described in Example 5 was employed except that 13.1 g(42.5 mmoles) of 10- undecenyl-p-tolyl sulfone and 14.0 g (85 mmoles) oftrimethyltin hydride were the reactants. The reaction mixture wasirradiated for 189 hours. The excess trimethyltin hydride was allowed toevaporate from the reaction mixture under a flow of nitrogen. Theresidual oil weighed 15.5 g. One-half of the crude product waschromatographed on a column containing silica gel using toluene and 2%acetone in toluene as eluents. The product,11-(p-tolylsuflonyl)undecyltrimethylstannane, was obtained as an oil.The presence of both the sulfonyl and trimethyltin groups was indicatedby the strong infrared absorption bands at 1315 cm⁻¹, 1300 cm⁻¹, 1285cm⁻¹, 1140 cm⁻¹ (--SO₂ --) and 760 cm⁻¹ [(CH₃)₃ Sn--].

Nmr showed the following:

The aromatic protons appeared as two multiplets each centered at 771 and728 Hz (2 protons each); the protons alpha to the sulfonyl moietyconsisted of a multiplet centered at 300 Hz (2 protons); the methylprotons of the tolyl group appeared as a singlet at 240 Hz (3 protons);the methylene [--(CH₂)₉ --] appeared as a broadened multiplet with peakmaxima at 161 and 119 Hz (18 protons); the methylene protons alpha tothe tin atom appeared as a triplet centered at 76 Hz (2 protons); theprotons of the trimethyltin group appeared as a singlet at 0 Hzaccompanied by one satellite band on either side (9 protons).

Analysis: Calc'd for C₂₁ H₃₈ O₂ SSn (percent): C, 53.29; H, 8.09. Found:C, 53.81; H, 8.09.

EXAMPLE 8

Using the procedures and apparatus described above and detailed inExamples 1 and 2, additional organotin compounds of this invention wereprepared and, along with the products of Examples 1-7, are identified inTable I below wherein the expression "high vacuum" denotes a pressure ofat least 0.1 mm Hg. Table I also indicates those instances where asolvent was used and/or the compound was purified as well as the meltingpoint or boiling point at a given pressure in millimeters of mercury.All of the compounds are identified as stannanes since they can beregarded as substitution products of "stannane," i.e., SnH₄.

The compounds identified by numbers 1-17, 21-23, 25-34, 36, 39-42,44-47, 49-56, 58-60 and 63-92 are deemed to be novel and to be unobviousover the prior art. The other compounds are either anticipated in theprior art or deemed to be so nearly like prior art compounds as to beobvious variants thereof. The prior art referred to in the two precedingsentences consists of:

J. appl. Chem. 9, 106-113 (1959);

C. a. 68, 1190 h (1968);

Ayrey et al., supra;

Ziegler British Pat. No. 966,813;

Bublitz U.S. Pat. No. 3,591,614;

Bublitz U.S. Pat. No. 3,641,037;

German Pat. No. 1,158,974;

J. appl. Chem. 9, 176 (1959);

J. appl. Chem. 7, 356 (1957);

Diss. Abstr. 22, 73 (1961);

as well as the art referred to herein under Background of the Invention.

                                      Table I                                     __________________________________________________________________________     ##STR23##                                                                                                                       Purifi-                                                                            m.p. or                                                             Reaction                                                                           cation                                                                             b.p. ° C.      No.                                                                              Stannane Compound                                                                           R'  n X                      Solvent                                                                            Method                                                                             (mm                   __________________________________________________________________________                                                            Hg)                   1  2,2'-sulfonylbisethyl-                                                                      H   1 SO.sub.2 CH.sub.2 CH.sub.2 Sn(CH.sub.3).sub.3                                                        none recry-                                                                             78.5-                    trimethyl-                                      stall'n                                                                            80.5                  2  2,2'-sulfonylbisethyl                                                                       H   1 SO.sub.2 CH.sub.2 CH.sub.2 Sn(CH.sub.3).sub.3                                                        benzene                                                                            recry-                                                                             78.3-                    trimethyl-                                      stall'n                                                                            79.3                  3  trimethyl-2-(methyl-                                                                        H   1 SO.sub.2 CH.sub.3      none recry-                                                                             51-53                    sulfonyl)ethyl-                                 stall'n                    4  2-(ethylsulfonyl)ethyl-                                                                     H   1 SO.sub.2 C.sub.2 H.sub.5                                                                             toluene                                                                            distil-                                                                            98-108                   trimethyl-                                      lation                                                                             (0.1-.2)              5  trimethyl-2-(i-pro-                                                                         H   1 SO.sub.2 -i-C.sub.3 H.sub.7                                                                          none distil-                                                                            90-98                    pylsulfonyl)ethyl-                              lation                                                                             (0.01)                6  2-(s-butylsulfonyl)-                                                                        H   1 SO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                               none distil-                                                                            96-99                    ethyltrimethyl-                                 lation                                                                             (0.06)                7  trimethyl-2-(t-pen-                                                                         H   1 SO.sub.2 C(CH.sub.3).sub.2 CH.sub.2 CH.sub.3                                                         none distil-                                                                            97-102                   tylsulfonyl)ethyl-                              lation                                                                             (0.07-0.09)           8  trimethyl-2-(n-octyl-                                                                       H   1 SO.sub.2 -n-C.sub.8 H.sub.17                                                                         none high oil                      sulfonyl)ethyl-                                 vacuum                     9  2-(n-dodecylsulfonyl)-                                                                      H   1 SO.sub.2 -n-C.sub.12 H.sub.25                                                                        toluene                                                                            high oil                      ethyltrimethyl                                  vacuum                     10 trimethyl-2-(n-octa-                                                                        H   1 SO.sub.2 -n-C.sub.18 H.sub.37                                                                        toluene                                                                            recry-                                                                             55-55.5                  decylsulfonyl)ethyl-                            stall'n                    11 2-(cyclohexylsulfonyl)- ethyltrimethyl-                                                     H   1                                                                                ##STR24##             none distill- lation                                                                    140-50 (.07-.15)      12 2-(benzylsulfonyl)- ethyltrimethyl-                                                         H   1                                                                                ##STR25##             aceto- nitrile                                                                     high vacuum                                                                        oil                   13 trimethyl-2-(phenyl- sulfonyl)ethyl-                                                        H   1                                                                                ##STR26##             none high vacuum                                                                        oil                   14 2-(p-t-butylphenylsul- fonyl)ethyltrimethyl-                                                H   1                                                                                ##STR27##             toluene                                                                            recry- stall'n                                                                     118-20                15 2-(p-chlorophenylsul- fonyl)ethyltrimethyl-                                                 H   1                                                                                ##STR28##             none recry- stall'n                                                                     57-60                 16 2-(2-piperidinoethylsul- fonyl)ethyltrimethyl, methiodide                                   H   1                                                                                ##STR29##             none ether wash                                                                         122-24                17 2,2'-(ethylenedisulfon-                                                                     H   1 SO.sub.2 (CH.sub.2).sub.2 SO.sub.2 (CH.sub.2).sub.2                            Sn(CH.sub.3).sub.3    ethyl                                                                              recry-                                                                             141.5                    yl)-bisethyltrimethyl-                     acetate                                                                            stall'n                                                                            (decomp.)             18 2-ethoxyethyltrimethyl-                                                                     H   1 OC.sub.2 H.sub.5       none distil-                                                                            80-82                                                                    lation                                                                             (50)                  19 2-n-butoxyethyltrimethyl-                                                                   H   1 O-n-C.sub.4 H.sub.9    none distil-                                                                            86-91                                                                    lation                                                                             (15)                  20 2-butoxyethyltrimethyl-                                                                     H   1 OCH.sub.2 CH(CH.sub.3).sub.2                                                                         none distil-                                                                            95-98                                                                    lation                                                                             (30)                  21 trimethyl-2-i-octoxyethyl-                                                                  H   1 O-i-C.sub.8 H.sub.17   none distil-                                                                            58-62                                                                    lation                                                                             (0.05)                22 2-decoxyethyltrimethyl-                                                                     H   1 OC.sub.10 H.sub.21     none distil-                                                                            68-71                                                                    lation                                                                             (0.03)                23 2-dodecoxyethyltrimethyl-                                                                   H   1 OC.sub.12 H.sub.25     none distil-                                                                            113-17                                                                   lation                                                                             (.07)                 24 3-(2,3-epoxypropoxy)- propyltrimethyl-                                                      H   2                                                                                ##STR30##             none distil- lation                                                                     100-2 (4.5)           25 2,2'-oxybisethyltri-                                                                        H   1 OCH.sub.2 CH.sub.2 Sn(CH.sub.3).sub.3                                                                none distil-                                                                            55-58                    methyl-                                         lation                                                                             (0.1)                 26 3,3'-oxybispropyltri-                                                                       H   2 OCH.sub.2 CH.sub.2 CH.sub.2 Sn(CH.sub.3).sub.3                                                       none distil-                                                                            74-5                     methyl-                                         lation                                                                             (0.07)                27 trimethyl-3-phenoxy- propyl                                                                 H   2                                                                                ##STR31##             none distil- lation                                                                     66-70 (0.025)         28 3-(p-t-butylphenoxy)pro- pyltrimethyl-                                                      H   2                                                                                ##STR32##             none distil- lation                                                                     98-100 (0.08)         29 trimethyl-3-(p-methoxy- phenoxy)propyl-                                                     H   2                                                                                ##STR33##             none distil- lation                                                                     98-100 (0.1)          30 3-(p-chlorophenoxy)pro- pyltrimethyl-                                                       H   2                                                                                ##STR34##             none distil- lation                                                                     84-88 (0.07)          31 2-(2,2,2-trifluoroethoxy)-                                                                  H   1 OCH.sub.2 CF.sub.3     none distil-                                                                            81-86                    ethyltrimethyl                                  lation                                                                             (50)                  32 2-(N,N-dimethylaminoeth-                                                                    H   1 OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                                 none distil-                                                                            43-43.5                  oxy)ethyltrimethyl-                             lation                                                                             (0.07-0.03)           33 2-(hexadecoxy)ethyltri-                                                                     H   1 OC.sub.16 H.sub.33     none high oil                      methyl-                                         vaccum                     34 2-(tetrahydro-1,1-dioxo 3-thienyloxy)propyltri- methyl-                                     H   2                                                                                ##STR35##             none high vacuum                                                                        oil                   35 trimethyl-3-phenylthio- propyl                                                              H   2                                                                                ##STR36##             none distil- lation                                                                     82.5-7 (0.06)         36 3,3'thiobispropyltri- methyl-                                                               H   2 SCH.sub.2 CH.sub.2 CH.sub.2 Sn(CH.sub.3).sub.3                                                       none distil- lation                                                                     94-98 (0.06)          37 2-(p-chlorophenylthio)- ethyltrimethyl-                                                     H   1                                                                                ##STR37##             none distil- lation                                                                     90-92 (0.07)          38 2-carbamoylethyltri- methyl-                                                                H   1                                                                                ##STR38##             tetrahy- drofuran                                                                  recry- stall'n                                                                     69-70.2               39 2-(N-t-butylcarbamoyl)- ethyltrimethyl-                                                     H   1                                                                                ##STR39##             tetrahy- drofuran                                                                  recry- stall'n                                                                     74-75.5               40 2-(N-hydroxymethylcar- bamoyl)ethyltrimethyl-                                               H   1                                                                                ##STR40##             tetrahy- drofuran                                                                  recry- stall'n                                                                     79-84                 41 N,N'-methylenebis(2- carbamoylethyltri- methyl-)                                            H   1                                                                                ##STR41##             aceto- nitrile                                                                     recry- stall'n                                                                     128-8.5               42 2-(hydrazinocarbonyl)- ethyltrimethyl-                                                      H   1                                                                                ##STR42##             ethanol                                                                            distil- lation                                                                     92-98 (0.07)          43 2-(ethoxycarbonyl)ethyl-                                                                    H   1 COOC.sub.2 H.sub.5     none distil-                                                                            85-6                     trimethyl-                                      lation                                                                             (10)                  44 2-(dodecoxycarbonyl)-                                                                       H   1 COO-n-C.sub.12 H.sub.25                                                                              none distil-                                                                            116-17                   ethyltrimethyl-                                 lation (0.003)             45 2,2'-(ethylenedioxydi-                                                                      H   1 COO(CH.sub.2).sub.2 OOC(CH.sub.2).sub.2 Sn(CH.sub.3                           ).sub.3                none distil-                                                                            122-30                   carbonyl)bisethyltri-                           lation                                                                             (0.07-0.1)               methyl-                                                                    46 trimethyl-3-ureido-                                                                         H   2 NHCONH.sub.2           tetrahy-                                                                           recry-                                                                             79.5-82                  propyl-                                    drofuran                                                                           stall'n                    47 trimethyl-3-thioureido-                                                                     H   2 NHCSNH.sub.2           tetrahy-                                                                           recry-                                                                             124.5-                   propyl-                                    drofuran                                                                           stall'n                                                                            125.5                 48 2-(N-carbazolyl)ethyl- trimethyl-                                                           H   1                                                                                ##STR43##             toluene                                                                            recry- stall'n                                                                     93.5- 95.5            49 trimethyl-2-(2-oxopyrro- lidinyl)ethyl-                                                     H   1                                                                                ##STR44##             none  distil- lation                                                                    69-80 (0.03)          50 2-(N-imidazolyl)ethyltri- methyl-                                                           H   1                                                                                ##STR45##             none distil- lation                                                                     85-6 (0.1)            51 2-(O,O-diethylphosphono)-                                                                   H   1 PO(OC.sub.2 H.sub.5).sub.2                                                                           none distil-                                                                            49.5-51                  ethyltrimethyl-                                 lation                                                                             (0.02)                52 3,3'-(carbonyldioxy)-                                                                       H   2 OCOO(CH.sub.2).sub.3 Sn(CH.sub.3).sub.3                                                              none distil-                                                                            104-108                  bispropyltrimethyl-                             lation                                                                             (0.05)                53 3-(2-furoyloxy)propyl- trimethyl-                                                           H   2                                                                                ##STR46##             none distil- lation                                                                     92-95 (0.1)           54 3-(N-methylcarbamoyloxy)                                                                    H   2 OCONHCH.sub.3          none distil-                                                                            78-81                    propyltrimethyl-                                lation                                                                             (0.15)                55 2-(2-pyridyl)ethyltri- methyl                                                               H   1                                                                                ##STR47##             none distil- lation                                                                     56 (0.1)              56 2-(2-methyl-5-pyridyl)- ethyltrimethyl-                                                     H   1                                                                                ##STR48##             none distil- lation                                                                     72-7 (0.05)           57 2-(4-pyridyl)ethyltri- methyl-                                                              H   1                                                                                ##STR49##             none distil- lation                                                                     63-66 (0.15)          58 4-(tetrahydro-1,1-dioxo- 2-thienyl)-3-hydroxy- butyltrimethyl-                              OH  2                                                                                ##STR50##             none recry- stall'n                                                                     99-103.5              59 2-(triethoxysilyl)- ethyltrimethyl-                                                         H   1 Si(OC.sub.2 H.sub. 5.sub.3                                                                           none distil- lation                                                                     56-7 (0.09)           60 2,2'-m-phenylenebispro- pyltrimethyl-                                                       CH.sub.3                                                                          1                                                                                ##STR51##             none distil- iation                                                                     110-11 (0.1)          61 2-cyanoethyltrimethyl-                                                                      H   1 CN                     none distil-                                                                            87-9                                                                     lation                                                                             (10)                  62 3-(hydroxypropyl)tri-                                                                       H   2 OH                     none distil-                                                                            37-8                     methyl-                                         lation                                                                             (0.1)                 63 2,2'-[2,4,8,10-tetraoxa- spiro[5.5]undec-3,9- ylene]-bisethyltrimethyl-       .             H   1                                                                                ##STR52##             none distil- lation                                                                     144 (0.0025)          64 2-ethoxy-2(O,O-diethyl-                                                                     OC.sub.2 H.sub.5                                                                  1 PO(OC.sub.2 H.sub.5).sub.2                                                                           none distil-                                                                            79                       phosphono)ethyltrimethyl-                       lation                                                                             (0.45-0.05)           65 2-(2,6,8-trimethyl-4- nonoxy)ethyltrimethyl-                                                H   1                                                                                ##STR53##             none distil- lation                                                                     67-71 (0.003)         66 2-(p-tolylsulfonyl)- ethyltrimethyl-                                                        H   1                                                                                ##STR54##             tetrahy- drofuran                                                                  recry- stall'n                                                                     55.5-58               67 2-(p-ethylphenylsulfonyl)- ethyltrimethyl-                                                  H   1                                                                                ##STR55##             tetrahy- drofuran                                                                  recry- stall'n                                                                     52-56.5               68 2-p-isopropylphenyl- sulfonyl)ethyltrimethyl-                                               H   1                                                                                ##STR56##              tetrahy- drofuran                                                                 recry- stall'n                                                                     53-57.5               69 2-(p-n-pentylphenylsul- fonyl)ethyltrimethyl-                                               H   1                                                                                ##STR57##             toluene                                                                            high vacuum                                                                        oil                   70 2-[p-(1,1-dimethylpro- pyl)phenylsulfonyl]- ethyltrimethyl-                                 H   1                                                                                ##STR58##             toluene                                                                            recry- stall'n                                                                     72-74                 71 2-(p-octylphenylsul- fonyl)ethyltrimethyl-                                                  H   1                                                                                ##STR59##             tetrahy- drofuran                                                                  high vacuum                                                                        oil                   72 2-(p-dodecylphenylsul- fonyl)ethyltrimethyl-                                                H   1                                                                                ##STR60##             tetrahy- drofuran                                                                  high vacuum                                                                        oil                   73 2-(p-n-dodecylphenylsul- fonyl)ethyltrimethyl-                                              H   1                                                                                ##STR61##             toluene                                                                            recry- stall'n                                                                     33-34                 74  2-(p-n-tridecylphenylsul- fonyl)ethyltrimethyl-                                            H   1                                                                                ##STR62##             toluene                                                                             recry- stall'n                                                                    43.3-44.8             75 2-(2,4-dimethylphenylsul- fonyl)ethyltrimethyl-                                             H   1                                                                                ##STR63##             tetrahy- drofuran                                                                  high vacuum                                                                        oil                   76 2-(2,5-dimethylphenyl- sulfonyl)ethyltrimethyl-                                             H   1                                                                                ##STR64##             tetrahy- drofuran                                                                  high vacuum                                                                        oil                   77 2-(2,4-diethylphenyl- sulfonyl)ethyltrimethyl-                                              H   1                                                                                ##STR65##             tetrahy- drofuran                                                                  high vacuum                                                                        oil                   78 2-(2,5-diisopropylphenyl- sulfonyl)ethyltrimethyl-                                          H   1                                                                                ##STR66##             tetrahy- drofuran                                                                  high vacuum                                                                        oil                   79 2-(p-cyclopentylphenyl- sulfonyl)ethyltrimethyl-                                            H   1                                                                                ##STR67##             tetrahy- drofuran                                                                  recry- stall'n                                                                     94-95                 80 2-(p-cyclohexylphenyl- sulfonyl)ethyltrimethyl-                                             H   1                                                                                ##STR68##             tetrahy- drofuran                                                                  recry- stall'n                                                                     116-118               81 2-(p-bicyclo[2.2.1]hept- 2-ylphenylsulfonyl)- ethyltrimethyl-                               H   1                                                                                ##STR69##             tetrahy- drofuran                                                                  recry- stall'n                                                                     106-110               82 2-(p-methoxyphenyl- sulfonyl)ethyltrimethyl-                                                H   1                                                                                ##STR70##             tetrahy- drofuran                                                                  recry- stall'n                                                                     35.5-39               83 2-(p-bromophenylsulfon- yl)ethyltrimethyl-                                                  H   1                                                                                ##STR71##             tetrahy- drofuran                                                                  recry- stall'n                                                                     84.5-86.5             84 2-(p-fluorophenylsul- fonyl)ethyltrimethyl                                                  H   1                                                                                ##STR72##             tetrahy- drofuran                                                                  recry- stall'n                                                                     65-66.5               85 2-(3,4-dichlorophenyl- sulfonyl)ethyltrimethyl-                                             H   1                                                                                ##STR73##             toluene                                                                            recry- stall'n                                                                     102.2-103.5           86 2-(2-naphthylsulfonyl)- ethyltrimethyl-                                                     H   1                                                                                ##STR74##             tetrahy- drofuran                                                                  recry- stall'n                                                                     88.5-90.7             87 4-[p-(1,1-dimethylethyl)- phenylsulfonyl]butyltri- methyl-                                  H   3                                                                                ##STR75##             none recry- stall'n                                                                     80-81.8               88 6-(p-tolylsulfonyl)- hexyltrimethyl                                                         H   5                                                                                ##STR76##             none column chroma-                                                                tography                                                                           oil                   89 11-(p-tolylsulfonyl)- undecyltrimethyl-                                                     H   10                                                                               ##STR77##             none column chroma-                                                                tography                                                                           oil                   __________________________________________________________________________

Compounds 90-92, and similar compounds in which n = 2 or more and X is--SO₂ R₁, -OR₇ or --SR₁₀, can be prepared by an alternative method fromthose shown above, the starting materials being: ##STR78## where Z ischlorine, bromine, or iodine; and

(b) AlkSO₂ R₁, AlkOR₇ or AlkSR₁₀, where Alk is sodium, potassium, orlithium.

Suitable type (a) starting materials include:

4-bromobutyltrimethylstannane;

3-chloropropyltrimethylstannane;

5-bromopentyltrimethylstannane;

6-chlorohexyltrimethylstannane;

7-bromoheptyltrimethylstannane;

8-iodooctyltrimethylstannane;

9-chlorononyltrimethylstannane;

10-bromodecyltrimethylstannane;

11-bromoundecyltrimethylstannane.

Suitable type (b) starting materials include: AlkSO₂ R₁ sodiumbenzenesulfinate;

sodium p-toluenesulfinate;

sodium p-ethylbenzenesulfinate;

sodium p-n-propylbenzenesulfinate;

sodium p-i-propylbenzenesulfinate;

sodium p-n-butylbenzenesulfinate;

sodium p-s-butylbenzenesulfinate;

sodium p-t-butylbenzenesulfinate;

sodium p-i-butylbenzenesulfinate;

sodium p-n-amylbenzensulfinate;

sodium p-t-amylbenzenesulfinate;

sodium p-n-hexylbenzenesulfinate;

sodium p-n-octylbenzenesulfinate;

sodium p-n-nonylbenzenesulfinate;

sodium p-n-decylbenzenesulfinate;

sodium p-n-undecylbenzenesulfinate;

sodium p-n-dodecylbenzenesulfinate;

sodium p-n-tridecylbenzenesulfinate;

sodium p-cyclohexylbenzenesulfinate;

sodium 2,4-dimethylbenzenesulfinate;

sodium 2,5-dimethylbenzenesulfinate;

sodium 2,4-diethylbenzenesulfinate;

potassium 2,5-diisopropylbenzenesulfinate;

potassium 2,4,6-trimethylbenzenesulfinate;

potassium p-methoxybenzenesulfinate;

potassium p-ethoxybenzenesulfinate;

potassium p-butoxybenzenesulfinate;

potassium 2,5-dimethoxybenzenesulfinate;

potassium 3,4-dimethoxybenzenesulfinate;

potassium p-methylthiobenzenesulfinate;

potassium p-butylthiobenzenesulfinate;

potassium 5-chloro-2-methoxybenzenesulfinate;

potassium 2-bromo-4-methoxybenzenesulfinate;

potassium 5-acetamido-2-methoxybenzenesulfinate;

potassium 5-nitro-2-methoxybenzenesulfinate;

potassium 2-methyl-4-methoxybenzenesulfinate;

potassium 2-methyl-5-chlorobenzenesulfinate

potassium p-fluorobenzenesulfinate;

potassium p-bromobenzenesulfinate;

potassium p-chlorobenzenesulfinate;

potassium 2,5-dichlorobenzenesulfinate;

potassium 2,4,5-trichlorobenzenesulfinate;

potassium trifluoromethylbenzenesulfinate;

potassium 3-nitrobenzenesulfinate

potassium 3,5-dichloro-2-hydroxybenzenesulfinate;

potassium p-acetamidobenzenesulfinate;

potassium p-carboxybenzenesulfinate;

potassium p-butoxycarbonylbenzenesulfinate;

potassium p-carbamoylbenzenesulfinate;

potassium p-cycanobenzenesulfinate;

potassium p-acetylbenzenesulfinate;

potassium 2-naphthalenesulfinate;

potassium p-phenylbenzenesulfinate;

potassium methanesulfinate;

potassium ethanesulfinate;

potassium 1-propanesulfinate;

potassium 2-propanesulfinate;

potassium 2-butanesulfinate;

potassium 2-pentanesulfinate;

potassium cyclohexanesulfinate;

lithium 1-octanesulfinate;

lithium 1-dodecanesulfinate;

lithium 1-octadecanesulfinate;

1,2-ethylenebis lithium sulfinate;

1,4-tetramethylenebis lithium sulfinate.

AlkOR₇

sodium methoxide;

sodium ethoxide;

sodium n-propoxide;

sodium t-butoxide;

sodium n-hexoxide;

sodium 2-ethylhexoxide;

sodium n-decoxide;

sodium n-dodecoxide;

sodium n-eicosoxide;

sodium n-stearyloxide;

sodium phenoxide;

lithium naphthoxide;

lithium p-ethylphenoxide;

lithium p-i-propylphenoxide;

lithium p-n-tridecylphenoxide;

lithium 2,4-dimethylphenoxide;

lithium 2,5-dimethylphenoxide;

lithium 2,4,5-trimethylphenoxide;

lithium p-methoxyphenoxide;

lithium p-n-butoxyphenoxide

lithium 3,4-dimethoxyphenoxide;

lithium p-n-octoxyphenoxide;

potassium p-chlorophenoxide;

potassium p-fluorophenoxide;

potassium p-bromophenoxide;

potassium 2,5-dichlorophenoxide;

potassium 2-methyl-5-chlorophenoxide;

potassium p-acetylphenoxide;

potassium 3-nitrophenoxide;

potassium p-methylthiophenoxide;

potassium 5-nitro-2-methoxyphenoxide;

potassium p-acetylphenoxide;

potassium cyclohexoxide.

AlkSR₁₀

sodium methylmercaptide;

sodium ethylmercaptide;

sodium n-propylmercaptide;

sodium i-propylmercaptide;

sodium n-butylmercaptide;

sodium s-butylmercaptide;

sodium t-butylmercaptide;

sodium n-pentylmercaptide;

sodium i-pentylmercaptide;

sodium s-pentylmercaptide;

sodium t-pentylmercaptide;

sodium n-hexylmercaptide;

sodium cyclohexylmercaptide;

sodium 4-methylcyclohexylmercaptide;

sodium n-octylmercaptide;

sodium t-octylmercaptide;

sodium benzylmercaptide;

sodium p-chlorobenzylmercaptide;

sodium phenylmercaptide;

sodium p-tolylmercaptide;

sodium p-ethylphenylmercaptide;

sodium p-n-propylphenylmercaptide;

sodium p-i-propylphenylmercaptide;

sodium p-n-butylphenylmercaptide;

sodium p-i-butylphenylmercaptide;

sodium p-s-butylphenylmercaptide;

sodium p-t-butylphenylmercaptide;

sodium p-n-pentylphenylmercaptide;

sodium p-t-pentylphenylmercaptide;

sodium p-n-hexylphenylmercaptide;

sodium p-n-heptylphenylmercaptide;

sodium p-n-octylphenylmercaptide;

sodium p-nonylphenylmercaptide;

sodium p-decylphenylmercaptide;

sodium p-dodecylphenylmercaptide;

sodium p-tridecylphenylmercaptide;

sodium p-cyclohexylphenylmercaptide;

sodium 2,4-dimethylphenylmercaptide;

sodium 2,5-dimethylphenylmercaptide;

sodium 2,4-diethylphenylmercaptide;

sodium 2,5-diisopropylphenylmercaptide;

sodium 2,4,6-trimethylphenylmercaptide;

sodium p-methoxyphenylmercaptide;

sodium p-ethoxyphenylmercaptide;

sodium p-butoxyphenylmercaptide;

sodium p-octoxyphenylmercaptide;

sodium 3,4-dimethoxyphenylmercaptide;

sodium p-methylthiophenylmercaptide;

sodium 5-chloro-2-methoxyphenylmercaptide;

sodium 2-chloro-4-methoxyphenylmercaptide;

sodium 3-bromo-4-methoxyphenylmercaptide;

sodium 2-nitro-4-methoxyphenylmercaptide;

sodium 2-methyl-4-methoxyphenylmercaptide;

sodium p-fluorophenylmercaptide;

sodium p-bromophenylmercaptide;

sodium p-chlorophenylmercaptide;

sodium 2,5-dichlorophenylmercaptide;

sodium 3,4-dichlorophenylmercaptide;

sodium 2,4,5-trichlorophenylmercaptide;

sodium trifluoromethylphenylmercaptide;

sodium 3-nitrophenylmercaptide;

sodium p-acetamidophenylmercaptide.

The specific preparative details for Compounds 90-92 are presentedbelow. The reaction times range from 0.5 to 24 hours and suitablereaction temperatures are from 20° to 120° C. The catalyst can be anyphase transfer catalyst as shown by E. V. Dehmlow, Chem. Tech. (1975),starting at page 210, which citation is hereby incorporated byreference.

EXAMPLE 9 (Compound 90)

Into a 125 ml single-necked round bottom flask fitted with a tefloncoated magnetic stir bar and a reflux condenser was charged 4.45 g ofsodium p-toluenesulfinate, 20 ml water, 10 ml toluene, 7 g of 75%4-bromobutyltrimethylstannane and 0.44 g oftri-n-butylhexadecylphophonium bromide. The mixture was refluxed for 2.5hours with rapid stirring. On cooling, the organic phase was separated,dried over anhydrous magnesium sulfate and stripped of solvent on arotary evaporator. The oil residue was distilled two times through ashort path distillation head. The second distillation afforded 3.3 g of4-(-p-tolylsulfonyl)butyltrimethylstannane, b.p. 136°-140° C. (1× 10⁻³mm Hg). The presence of both the sulfonyl and trimethyltin moieties wasindicated by strong infrared absorption bands at 1315 cm⁻¹, 1300 cm⁻¹,1142 cm⁻¹ (--SO₂ --) and 765 cm⁻¹ [(CH₃)₃ Sn--]. NMR spectroscopy showedthe following:

The aromatic protons appeared as two multiplets each centered at 768 Hzand 726 Hz (each having 2 protons); the proton alpha to the sulfonylgroup appeared as a complex multiplet centered at 291 Hz (2 protons);the beta and gamma methylene protons appeared as a complex multipletcentered at 157 Hz (4 protons); the p-tolyl methyl group appeared as asinglet at 244 Hz (3 protons); the methylene proton adjacent to the tinatom appeared as a complex multiplet centered at 74 Hz (2 protons); theprotons of the trimethyltin group appeared as a singlet, flanked oneither side by satellite bands, at -4 Hz from the tetramethylsilaneinternal standard (9 protons).

Analysis: Calc'd for C₁₄ H₂₄ O₂ SSn (percent): C, 44.83; H, 6.45; S,8.55; Sn, 31.64. Found: C, 44.98; H, 6.61; S, 8.46; Sn, 31.65.

EXAMPLE 10 (Compound 91)

Into a 100 ml single-necked round bottom flask fitted with a tefloncoated magnetic stir bar and a reflux condenser was charged 7.68 g of a1:1 mixture of 4-bromobutyltrimethylstannane and4-chlorobutyltrimethylstannane, 15 ml of toluene, 5 g ofp-t-butylthiophenol, 1.2 g of sodium hydroxide, 20 ml water and 0.44 gof tri-n-butylhexadecylphosphonium bromide. The mixture was refluxed for1/2 hour. On cooling, the phases were separated and the water layerextracted with toluene. The organic phase was combined with the extractand washed once with water and dried over anhydrous magnesium sulfate.Solvent was stripped on a rotary evaporator. The product was distilledthrough a short-path distillation head giving 7.36 g of liquid,4-(p-t-butylphenylthio)butyltrimethylsannane, b.p. 116°-121° C. (1 ×10⁻³ mm). The presence of the trimethyltin moiety was indicated by astrong infrared absorption band at 760 cm⁻¹. NMR spectroscopy showed thefollowing:

The aromatic protons appeared as a singlet at 717 Hz (4 protons); theprotons alpha to the thio group appeared as a multiplet centered at 282Hz (2 protons); the beta and gamma methylene protons appeared as amultiplet centered at 160 Hz (4 protons); the methyl protons of thet-butyl group appeared as a singlet at 130 Hz (9 protons); the methyleneprotons adjacent to the tin atom appeared as a complex multipletcentered at 91 Hz (2protons); the protons of the trimethyltin groupappeared as a singlet flanked on either side by satellite bands at 3 Hz(9 protons) from the tetramethylsilane internal standard.

Analysis: Calc's for C₁₇ H₃₀ SSn (percent): C, 53.01; H, 7.85; S, 8.32;Sn, 30.81. Found: C, 53.28; H, 8.24; S, 8.28; Sn, 29.98.

EXAMPLE 11 (Compound 92)

In the manner described for Compound #91, a mixture of 10.57 g. of 75%4-bromobutyltrimethylstannane, 10 ml of toluene, 2.98 g of thiophenol,1.08 g of sodium hydroxide, 20 ml of water and 0.44 g oftri-n-butylhexadecylphosphonium bromide were heated at 40° C. for 1/2hour. The crude product was distilled through a short path head giving6.14 g of a liquid, 4-(phenylthio)- butyltrimethylstannane, b.p. 95°-97°C. (0.02 mm). The presence of the trimethyltin moiety was indicated by astrong infrared absorption band at 760 cm⁻¹. NMR spectroscopy showed thefollowing:

The aromatic protons appeared as a complex multiplet centered at 713 Hz(5 protons); the protons alpha to the thio group appeared as a tripletcentered at 284 Hz (2 protons); the beta and gamma protons appeared as acomplex multiplet centered at 160 Hz (4 protons); the methylene protonsadjacent to the tin atom appeared as a complex multiplet centered at 89Hz (2 protons); the protons of the trimethyltin group appeared as asinglet flanked on either side by satellite bands at 4 Hz (9 protons)from the tetramethylsilane internal standard.

Analysis: Calc'd for C₁₃ H₂₂ SSn (percent): C, 47.44; H, 6.74; S, 9.74;Sn, 36.07. Found: C, 47.46; H, 6.77; S, 9.29; Sn, 35.43.

EXAMPLE 12

The organotin compounds of this invention were tested as insecticidesand herbicides according to the following procedures:

A. Mosquito Larvae Test

Formulations were prepared by dissolving 30 mg of organotin compound ofthe invention in 10 ml of acetone. This solution was then diluted to 1ppm with water. Two 25-ml aliquots were placed in test tubes to whichwere added 10 to 25 fourth instar larvae of the yellow fever mosquito,Aedes aegypti (Linnaeus). The tubes were held in darkness for 72 hours.At the end of this period the percent control was determined.

B. Aphid Contact Test

Test formulations were prepared for spraying at 1000 ppm (parts permillion) concentration by dissolving them in a small amount of acetoneand adding a suitable wetting agent. Typically, 0.6 gram of organotincompound was dissolved (or suspended) in 10 ml of acetone, 2 drops ofTriton-X100 wetting agent (octylphenoxy polyethoxy ethanol with 9-10mole percent of polyethylene oxide) were added and this was suspended in300 ml of water to make a 6000 ppm suspension. An aliquot was thenfurther diluted with distilled water to 1000 ppm concentration oforganotin compound.

Eight to ten day old barley seedlings, grown ten plants each in a 12 oz.cup, were infested with corn leaf aphids Rhopalosiphum maidis (Fitch), 2days prior to treatment. Two pots were treated with each formulation byspraying with a spray atomizer while the plants were rotating on aturntable. Following treatment, the plants were held for 5 days in thegreenhouse. At the end of this period, the percent control of the aphidswas estimated based on the reduction of the population density ascompared to untreated plants used as controls.

C. Tobacco Bud Worm Diet Test

Test formulations were prepared at 1000 ppm as in B, the Aphid ContactTest, above. Two-tenths ml of the diluted formulations was pipetted ontothe surface of 5 grams of a synthetic diet mixture held in partiallyfilled cells of a plastic jelly tray. Five cells were treated with eachchemical dilution. The diet mixture was a modified Vanderzant dietconsisting of wheat germ, soy flour, agar, sugar, salts, vitamins,preservatives and water. The jelly trays had fifty cavities per sheet,each cavity being approximately 2.5 × 4.0 × 1.5 cm.

Following treatment, a third or early fourth instar larva of the tobaccobud worm, Heliothis virescens (Fabricius), was placed in each cell. Thetrays were then covered with a plastic film plus a sheet of rigid platicand were held in an incubator at 80° F.

At the end of one week, the trays were examined and the percent controlwas determined, adjusted for any natural mortality in the controls byAbbott's formula. The trays were held an additional week and anyabnormalities in the development of the survivors was noted.

D. Cottom Boll Weevil Test

Formulations were prepared at 1000 ppm as in B, the Aphid Contact Test,above. Cottom seedlings 12 to 14 days old grown in 12 oz cups were used.Two pots were treated with each formulation by spraying with a sprayatomizer while rotating the pots on a turntable. Five adult cotton bollweevils, Anthonomous grandis Boheman, were placed in each pot followingtreatment and were caged by covering the pots with an inverted 16 ozstyrofoam cup with small perforations punched in the bottom. Thesurviving weevils were counted after five days in the greenhouse todetermine the percent control, corrected for any natural mortality inthe control plants by Abbott's formula. The percent reduction in feedingwas estimated by visual comparison of the feeding damage to the treatedplants with the control (untreated) plants.

E. Mite Contact Test

The formulations used were prepared at 1000 ppm as in B, the AphidContact Test, above.

Cotton in the second primary leaf stage, grown in 12 oz cups undergreenhouse conditions at 70°-75° F. was used in this test. One plant(two primary leaves) in one pot was used for each replicate and tworeplicates were used for each organotin compound tested. A 1-inchdiameter circle of tree tanglefoot, a sticky, non-toxic preparation, wasused to confine the mites to the upper leaf surfaces. Approximately 25adult two spotted spider mites, Tetranychus urticae Koch, weretransferred to each test plant 24 hours prior to treatment.

The infested plants were sprayed with the dispersions using a smallspray atomizer to thoroughly drench the foliage. The plants werereturned to the greenhouse where they were held for 6 days. After thisperiod, the plants were examined for adult live mites remaining on theleaves. On an estimation basis and in comparison with the number ofliving mites on the control plants, the percent control was determined.

F. Mite One-Day Residual Test

Test compounds were prepared as in B, the Aphid Contact Test, above butwere further diluted to 500 ppm with water.

Cotton, in the second primary leaf stage grown in twelve ounce cupsunder greenhouse conditions at 70°-75° F., was used in the test.

One plant (two primary leaves) in one pot was used for each replicate;two replicates were used for each concentration of organotin compoundtested.

The plants were sprayed with the dispersions using a small sprayatomizer to thoroughly drench the foliage.

One day following treatment, a circle of tree tanglefoot was placed onthe upper surface of the treated leaves and adult mites, Tetranychusurticae Koch, were transferred into this confinement.

Six days following infestation with mites, the plants were examined foradult live mites remaining on the leaves. On an estimation basis incomparison with the number of living mites on the control plants, thepercent control was determined.

G. Abbott's Formula: ##EQU1##

The results of the above-described tests are set forth in Table II belowwherein the compound numbers correspond to those in Table I above.

                                      Table II                                    __________________________________________________________________________    Organotin Compounds as Insecticides                                                  % Control   % Control                                                                           % Control                                                                              Boll Weevil       Mite                             Mosquito                                                                            % Control                                                                           Tobacco                                                                             Cotton   % Feeding         One-Day                   Compound                                                                             Larvae                                                                              Aphids                                                                              Bud Worm                                                                            Boll Weevil                                                                            Reduced  Mite Contact                                                                           Residual                  No.    1 PPM 1000 PPM                                                                            1000 PM                                                                             1000 PPM on Cotton                                                                              1000 PPM 500                       __________________________________________________________________________                                                        PPM                       1 (and 2)                                                                            100   100   100   100      100      100      100                        3      60   100   100    87       80      --       100                        4      98   100   100    56      --       --       100                        5     0     100   100   100      --       --       100                        6      80   100   100    85      --       --       100                        7      75   100   100    71      --       --       100                        8     100   100   100   100      100      --       100                        9     100   100   *     100      100      --        90                       10      80   0     100    67       90      --        25                       11     100   100   100   100      100      100      --                        12      95   100   100    67       90      --       100                       13     100   100   100   100        94     100      **                         * 100% Control at 100 ppm; not tested at 1000 ppm.                            ** 100% Control at 100 ppm; not tested at 500 ppm.                       

    14     100   100   100   100       95      --       100                       15     100   100   100   100      100      --       100                       16      15   100   100    56       70      --        95                       17     100    95   100    56       80      --        80                       18     100    20   100    28       50      --        25                       19     100    30   100    56       90      --        90                       20     100   0     100    28       40      --        50                       21     100    95   100    67       90      --        40                       22     100   100   100   100      100      --        95                       23     100   100   100    85       95      --       100                       24     100   0     100    43       70      --        30                       25     100   0     100   100       95      --       0                         26     100    30   100   100       95      --        25                       27     100   100   100    57       70      --       0                         28     100   100   100   100      100      --       100                       29     100   100   100    90      100      --       100                       30     100    90   100   100      100      --       100                       31     100    60   100    30       50      --        25                       32      60   100   100    57       90      --        90                       33     100   100   100   100      100      --       100                       34     100   100   100    44       70      100      **                        35     100***                                                                              100   100    75       80      --       100                       36     100   100   100   100       95      --       100                       37     100   100   100   100      100      --       100                        ** 100% Control at 100 ppm; not tested at 500 ppm.                            *** 100% Control at 0.001 ppm.                                           

    38     100   100   100    44       80      --       100                       39     100   100   100    75       80      --        50                       40     0     100   100    50       70      --       100                       41     100   100   100   100      100      --       100                       42     0     100   100    63       70      --       100                       43     100   0     100    71       90      --       0                         44      70   100   100    75       80      --       100                       45     100   100   100   100      100      --       100                       46     0     100   100    22       70      100      --                        47      15   100   100    85       95      --       100                       48     100   100   100    29       95      --       100                       49     100   100   100    71       90      --       100                       50     0     100   100   100       95      --       100                       51     100   100   100    85       95      --        95                       52     100   100   100   100      100      --       100                       53     100    95   100   100       90      --       100                       54     100   100   100    57       70      --       100                       55     100   100   100    44       70      --        50                       56     100   100   100   100       95      --       100                       57     100   100   100    89       95      --        80                       58     0      97   100    56       80      100      **                        59     100    30   100    71       80      --       0                         60     100    20   100    89       95      --       0                         61     100   100   100    22       50      --        90                        ** 100% Control at 100 ppm; not tested at 500 ppm.                       

            % Control     % Control                                                                              % Control Boll Weevil                                                                            Mite                                Mosquito                                                                             % Control                                                                            Tobacco  Cotton    % Feeding                                                                              One-day                     Compound                                                                              Larvae Aphids Bud Worm Boll Weevil                                                                             Reduced  Residual                    No.     1 PPM  1000 PPM                                                                             1000 PPM on Cotton 500 PPM                              __________________________________________________________________________    62      100     95    100       85        90       45                         63      100    100    100      100        90      100                         64      0      100    100       56        80      100                         65      100     75    100       80       100       50                         66      100    100    100      100       --       100                         67      100    100    100       88       100      100                         68      100    100    100       88       100      100                         69      100    100    100       78        95      100                         70      100    100    100      100       100      100                         71      100    100    100       90        50      100                         72      100     90    100      100        50      100                         73      100     90    100      100        95      100                         74      100    0      100      100       100      100                         75      100     95    100       80       100      100                         76      100    100    100      100        90      100                         77      100    100    100      100       100      100                         78      100    100    100      100       100      100                         79      100     20    100      100       100      100                         80      100     93    100       90        95      100                         81      100     60    100      100       100      100                         82       75    100    100       75       100      100                         83       15    100    100       75       100      100                         84       86     97    100      100       100      100                         85      100     95    100      100       100      100                         86      100    100    100       90       100      100                         87      100     95    100       87        95      100                         88      100    100    100      100       100      100                         89      100     80     60      100       100      100                         90      100    100    100       90       100      100                         91      100    100    100       90       100      100                         92      100     95    100       90       100       90                                           % Control   % Control                                                                           % Control                                                                             Boll Weevil                                                                           Mite                                        Mosquito                                                                            % Control                                                                           Tobacco                                                                             Cotton  % Feeding                                                                             One-Day                                     Larvae                                                                              Aphids                                                                              Bud Worm                                                                            Boll Weevil                                                                           Reduced Residual                  Comparative Data  1 PPM 1000 PPM                                                                            1000 PPM                                                                            1000 PPM                                                                              on Cotton                                                                             500                       __________________________________________________________________________                                                        PPM                       Stamm et al. 3,206,489                                                                          55    95     20    40      90      80                        ##STR79##                                                                    2-Thioacetoxyethyltri-n-butyltin                                              Koopmans et al. 3,031,483                                                                        0    98    100   100     100     100                        ##STR80##                                                                    Trimethyltin p-toluenesulfinate                                               __________________________________________________________________________

The Stamm et al. compound, for which data are presented at the end ofTable II, was prepared in accordance with Example 1 of the Stamm et al.patent. The Koopmans et al. compound, for which data are similarlypresented, was prepared as follows.

In a 250 ml Erlenmeyer flask was placed a solution of 5.95 g. (0.033mole) of ##STR81## in 50 ml. H₂ O. Then 6.6 g. (0.033 mole) (CH₃)₃ SnClin 100 ml. acetone was added dropwise. A white precipitate formed. Thereaction mixture was heated to 60° C. for 20 minutes. After stirringovernight, the acetone was removed by evaporation and a white viscousresidue separated. The water layer was decanted. The viscous residue wastreated with 50 ml. of petroleum ether. A solidified product (8.1 g.),having a m.p. of 98°-102° C., was isolated. Peter M. Slegen, Univ. ofNorth Carolina, Ph.D. thesis 1967, reported m.p. 97°-101° C. fortrimethyltin p-toluenesulfinate. The I.R. exhibited strong absorption at955 cm⁻¹ and 990 cm⁻¹.

As can be seen from the results set forth in Table II above, theorganotin compounds of the invention exhibit good to superiorinsecticidal activity for a wide variety of insects, especially incomparison with the two prior art compounds.

In all of the following examples, the numbered compounds correspond tothose set forth in Table I above.

EXAMPLE 13 Mite One-Day Residual Test of Organotin Compounds atDifferent Formulation Concentrations

In this example, test formulations were prepared to contain differentconcentrations of several representative organotin compounds of theinvention. The method employed was as follows:

Cotton in the second primary leaf stage, grown in 12 ounce cups undergreenhouse conditions at 70°-75° F. was used in this test. One plant(two primary leaves) in one pot was used for each replicate and tworeplicates were used for each concentration of tin compound tested. Testformulations were prepared by dissolving 50 mgs. of tin compound in oneml of acetone, adding one drop of Emulfor 719, a commercialsurface-active dispersing agent (polyoxyethylated vegetable oil) andsuspended in 50 ml of water for concentration of 1000 ppm (parts permillion). Aliquots of this solution were further diluted with distilledwater to concentrations of 100, 20 and 5 ppm. The plants were sprayedwith the formulations using a small spray atomizer to thoroughly drenchthe foliage. One day following treatment, a circle of tree tanglefootwas placed on the upper surfaces of the treated leaves and adult mites,Tetranychus urticae Koch, were transferred into this confinement. Countsof these mites were made immediately following transfer and again 6 dayslater.

Abbott's formula was used to compensate for check mortality and toobtain the adjusted percent control. The results are shown in Table IIIbelow:

                  Table III                                                       ______________________________________                                        Mite One-Day Residual Test                                                            % Control                                                             Compound  100 PPM     20 PPM      5 PPM                                       ______________________________________                                         1        100         99          63                                          14        100         68          49                                          23         94         45          44                                          41        100         87          57                                          ______________________________________                                    

The results above clearly indicate that the selected organotin compoundsof the invention exhibit a high degree of effectiveness at differentlevels of concentration.

EXAMPLE 14 Tobacco Bud Worm -- Cotton Test

The test formulations in this example were also prepared to containdifferent concentrations of representative compounds of the inventionwhich were then tested according to the procedure described below:

Test formulations were prepared by dissolving 50 mg of organotincompound of the invention in one ml of acetone, adding one drop ofEmulfor 719, a commercial surface-active dispersing agent(polyoxyethylated vegetable oil) and suspended in 50 ml of water for aconcentration of 1000 ppm (parts per million). Aliquots of the solutionwere further diluted with distilled water to concentrations of 100, 20and 5 ppm.

Cotton seedlings two weeks old were used. These were grown in 12 ouncecups with two plants in each cup. The diluted formulations were appliedto the seedling plants with a spray atomizer and allowed to dry. Threecups were treated with each diluted formulation. A third instar larvaeof the tobacco bud worm, Heliothis virescens (Fabricius), was placed ineach cup and confined by inverting a perforated 16 oz. styrofoam cupover the top. Percent control of the worms was determined after twoweeks in the greenhouse.

The results of this test are set forth in Table IV below:

                  Table IV                                                        ______________________________________                                        Tobacco Bud Worm on Greenhouse Cotton                                                   % Control                                                           Compound No.                                                                              100 PPM    20 PPM     5 PPM                                       ______________________________________                                         1          100        100        100                                         14          100        100        50                                          23           66         50        0                                           36          100         33        66                                          41          100        100        0                                           45          100        100        0                                           52          100         0         0                                           56           66         33        0                                           ______________________________________                                    

As can be seen from the results shown in Table IV above, the organotincompounds of the invention are generally excellent in controlling thistype of insect.

EXAMPLE 15 Aphid -- Soil Drench Test

This example is similar to Examples 7 and 8 above in that testformulations containing different concentrations of representativeorganotin compounds were prepared and then tested according to thefollowing procedure:

Test formulations were prepared by dissolving 10 mg of organotincompound of the invention in one ml of acetone plus one drop (about 30mg) of Emulfor 719, the same surface-active agent identified in Example9 above, and diluting with water to 100 ml for a concentration of 100ppm of the test organotin compound in water. Further dilutions were madeto 10 ppm and 1 ppm with water.

Barley seedlings eight days old, grown in 12 oz. cups, 10 plants percup, with a total weight, including the soil, of approximately 440grams, were used. The seedlings were deliberately infested with cornleaf aphids, Rhopalosiphum maidis (Fitch), a day prior to treatment.Twenty-two ml aliquots of the dilute formulations were drenched on thesurface of the cups, but not over the infested plant parts. Two cupswere treated with each rate. Rates were calculated in pounds per acrebased on a weight of 440 gms/cup and assuming an acre of soil 7 inchesdeep weighs two million pounds.

The percent control was determined by observations made one weekfollowing treatment. The results are set forth in Table V below wherein"#/A" denotes the calculated pounds per acre.

                  Table V                                                         ______________________________________                                        Barley Soil Drench                                                            Compound   % Control of Aphids                                                No.        10#/A      1#/A       0.1#/A                                       ______________________________________                                         1         100        93         86                                           14          86        30          0                                           23          95        86         78                                           45         100        99          0                                           52         100        80         40                                           56         100        97         70                                           ______________________________________                                    

This test demonstrates that the chemicals of this invention are alsoeffective as systemic insecticides on barley plants in that they absorbsufficient amounts of the organotin compounds of the invention toeffectively control aphids.

EXAMPLE 16 Organotin Compounds as Preemergence Herbicides

This example illustrates the use of the organotin compounds of theinvention as preemergence herbicides. Six hundred mg of organotincompound was dissolved in 10 ml of an organic solvent (e.g., acetone) towhich 30 mg of a commercial emulsifying agent (e.g., isooctyl polyethoxyethanol, "Triton X100") was added. The solution was diluted to 100 mlwith distilled water. Twenty milliliters of this 6000 ppm solution wasfurther diluted to 250 ppm with distilled water. The solution wasapplied at the rate of 10#/A (pounds per acre) by drenching 46 ml of the250 ppm solution on the surface of soil compound in 41/2 inch plasticpots which had been planted with the following weeds: rough pigweed,Amaranthus retroflexus L.: purslane, Portulaca oleracea L.; orjimsonweed, Datura stramonium L.; tall morningglory, Ipomea purpurea(L.) Roth; crabgrass, Digitaria ischaemum (Schreb.) Muhl.;barnyardgrass, Echinochloa crusgalli (L.) Beauv.; giant foxtail, Setariafaberi Herm.; and southern nutsedge, Cyperus rotundus L. The percentcontrol of the weeds as compared to untreated weeds used as checks wasdetermined two weeks after treatment. Table VI data below show theefficacy of the compounds of the invention as preemergence herbicides.

                                      Table VI                                    __________________________________________________________________________    Organotin Compounds as Preemergence Herbicides                                                   Purslane (p)                                                                          Wild          Giant                                                                             Barnyard                         Compound No.                                                                          Rate Lb/A                                                                           Pigweed                                                                            or Jimsonweed                                                                         Morning glory                                                                         Crabgrass                                                                           Foxtail                                                                           Grass                            __________________________________________________________________________     1      10    100   100p   100     100   100 100                               3      10    100  100     100     100   100 100                               4      10    100  100     100     100   100 100                               5      10    100  100     100     100   100 100                               6      10    100  100     100     100   100 100                               7      10    100  100     100     100   100 100                               8      10    100  100     100     100   100 100                               9      10    100  100     10      15    30  20                               11      10    100   100p   100     100   100 100                              12      10    100  100     100     100   100 100                              13      20    100   100p   100     100   100 100                              14      10    100  100     98      100   100 80                               15      10    100  100     100     100   100 100                              16      10    100  100     100     100   100 100                              17      10    100  100     50      100   100 100                              18      10    100  100     100     100   100 100                              19      10    100  100     100     100   100 100                              20      10    100  100     100     100   100 100                              21      10    100  100     95      85    60  100                              22      10    100   95     50      95    80  100                              23      10    100   50p    65      70    90  80                               24      10    100  100     100     100   100 100                              25      10    100  100     100     100   100 100                              26      10    100   98     0       50    95  0                                27      10     90   80     90      100   100 10                               28      10     0    0      0       0     0   0                                29      10    100  100     35      65    98  100                              30      10    100   0      25      0     98  100                              31      10    100   0      100     90    100 90                               32      10    100  100     100     100   100 100                              33      10    100  100     80      65    98  100                              34      10    100   100p   100     100   100 100                              35      10    100   80     20      90    100 60                               36      10     45   0      20      60    60  40                               37      10    100  100     100     100   100 100                              38      10    100  100     98      100   100 100                              39      10    100  100     100     100   100 100                              40      10    100  100     100     100   100 100                              41      10     85   0      0       80    0   0                                42      10    100  100     95      95    100 100                              43      10     65    0     0       0     0   99                               44      10    100   80     20      60    60  60                               45      10    100   90     35      75    0   98                               46      10    100   100p   100     100   100 100                              47      10    100  100     90      95    85  85                               48      10    100  100     0       100   100 45                               49      10    100  100     100     100   100 100                              50      10    100  100     100     100   100 100                              51      10    100  100     80      100   100 100                              52      10    100  100     95      100   90  100                              53      10    100  100     98      100   100 100                              54      10    100  100     30      100   100 100                              55      10    100  100     100     100   100 100                              56      10    100  100     30      100   100 100                              57      10    100  100     100     100   100 100                              58      10    100   100p   90      100   100 100                              59      10    100  100     100     100   100 100                              61      10    100   0      100     95    70  98                               62      10    100  100     85      95    85  98                               63      10     95   85     0       0     0   0                                __________________________________________________________________________

As can be seen from the results set forth in Table VI above, theorganotin compounds of the invention are generally excellent aspreemergence herbicides for a wide variety of weeds.

EXAMPLE 17 Organotin Compounds as Postemergence Herbicides

This example illustrates the effectiveness of the organotin compounds ofthe invention as postemergence herbicides. The 6000 ppm solutiondescribed in Example 10 above was obtained in the same manner andatomized with a conventional DeVilbiss sprayer wetting the foliage tothe drip point. The weeds, which were the same species as described inExample 10 above, were treated 6 days after emergence. The percentcontrol was evaluated 2 weeks after treatment. Table VII below shows theresults using compounds of the invention as postemergence herbicides.

                                      Table VII                                   __________________________________________________________________________    __________________________________________________________________________    Organotin Compounds as Postemergence Herbicides                                                  Purslane (p)                                                                          Wild          Giant                                                                             Barnyard                         Compound No.                                                                          Rate PPM                                                                            Pigweed                                                                            or Jimsonweed                                                                         Morning glory                                                                         Crabgrass                                                                           Foxtail                                                                           Grass                            __________________________________________________________________________    1       6000  100   100p   50      50    90  60                               3       6000  100   90     100     100   100 100                              4       6000  100  100     100     100   75  100                              5       6000  100   90     100     100   100 100                              6       6000  100  100     100     100   100 100                              7       6000  100  100     100     100   100 100                              8       6000  100  100     100     100   98  100                              9       6000  100   15     100     15    40  40                               10      6000  98    5      15      0     5   10                               11      6000  100  100     100     100   100 100                              12      6000  100  100     100     100   100 100                              13      6000  100   100p   100     100   100 100                              14      6000  98    65     95      15    5   30                               15      6000  100  100     100     30    35  75                               16      6000  100  100     100     50    95  98                               17      6000  100   15     100     65    25  40                               18      6000  75    15     30      5     0   15                               19      6000  20    5      25      15    15  15                               20      6000  15    20     80      10    0   10                               21      6000  10    0      30      10    5   0                                22      6000  30    0      75      20    10  5                                23      6000  100   0      98      5     5   25                               24      6000  90    25     75      15    0   10                               25      6000  100   50p    25      5     0   90                               26      6000  15    5      15      5     0   10                               27      6000  100   0      35      75    60  70                               28      6000  25    0      35      50    15  10                               29      6000  100   10     98      95    35  15                               30      6000  65    5      60      25    5   5                                31      6000  0     0      0       5     0   0                                32      6000  100   10     100     65    35  20                               33      6000  100   0      50      35    5   5                                34      6000  100  100p    100     100   100 100                              35      6000  95    25     90      60    70  60                               36      6000  100   25     95      40    50  60                               37      6000  100  100     100     100   100 100                              38      6000  100  100     100     100   100 100                              39      6000  100   30     45      35    5   15                               40      6000  90    20     40      50    80  80                               41      6000  100   0      75      0     0   15                               42      6000  95     20    95      50    80  80                               43      6000  65    5      10      0     0   0                                44      6000  95    0      25      20    20  25                               45      6000  100   5      75      25    75  75                               46      6000  100  100p    100     90    98  85                               47      6000  100   50     90      50    35  70                               48      6000  100   0      20      5     5   25                               49      6000  100  100     100     100   100 100                              50      6000  100  100     100     98    95  100                              51      6000  100  100     100     100   100 100                              52      6000  90    15     0       10    10  10                               53      6000  100   95     100     95    98  90                               54      6000  100  100     98      100   90  98                               55      6000  100   5      95      10    5   30                               56      6000  100  100     100     100   98  98                               57      6000  100  100     100     100   100 100                              58      6000  100   75p    85      80    60  70                               59      6000  90    15     25      5     0   10                               60      6000  98    10     5       5     5   10                               61      6000  100   0      20      0     0   10                               62      6000  98    80     75      15    5   35                               63      6000  100   20     90      80    65  80                               __________________________________________________________________________

The results in Table VII above reveal that the organotin compounds ofthe invention are also generally excellent as postemergence herbicidesfor a wide variety of weeds.

As is brought out above in the discussion of prior art under "Backgroundof the Invention," a Peterson sulfonyl compound was reported as beingsubject to hydrolysis on being exposed to air. The work reported in thefollowing Example serves as confirmation of this conclusion.

EXAMPLE 18

A. The compound subjected to humid air was a typical Peterson compound,phenylsulfonylmethyltrimethylstannane, ##STR82## A 5 gal. jar was set onits side on a wooden support and contained a wire meash screen tosupport samples in test over a mixture of 152 g of (NH₄)₂ SO₄ in 168 gof H₂ O. An excess of (NH₄)₂ SO₄ in contact with a saturated aqueoussolution of (NH₄)₂ SO₄ gives 81% humidity in a closed space.¹ Thefollowing samples of this Peterson compound were weighed into 40 mm O.D.petri dishes (minus cover) of 8 mm depth and the dishes placed into thehumidity chamber, and the chamber was then closed: #15 dish 0.2186 g;#34 dish 0.2006 g. Before the samples were removed from the balance, asolid crust began forming on the surface of the liquid and, inside of 10minutes, covered all of the liquid surface. An odor of a volatiletrimethyltin compound was noted. When the samples were placed in thehumidity chamber, the samples coated almost all of the surface areainside the dishes. The 5 gal. jar was set on the bench under normallaboratory lighting. The initial temperature inside the chamber was24.5° C. Over 4 days, the temperature ranged from the initialtemperature as a high to a low temperature of 18° C. The #15 sample wasremoved after 4 days. Under the surface crust, there was an oily solid.The sample was scraped with a spatula into a 2 dram sample vial. Theoily solid remaining was washed into the vial with chloroform (about 0.5to 1 ml). The chloroform was removed under a stream of nitrogen. The #34sample was removed from the chamber after 7 days. The sample wascompletely solid and was scraped into a vial. The NMR spectra for bothsamples showed that, in addition to the aromatic absorptions, there wasone singlet due to CH₃ of the hydrolysis product, ##STR83## at 307 Hzand a broadened singlet flanked by satellites at 36.5 Hz for (CH₃)₃ Snand a broadened singlet at 191 Hz for the OH. These results indicate theformation of a mixture of trimethyltin hydroxide and methylphenylsulfone. There was no unreacted starting Peterson compound.

B. A corresponding compound of this invention,phenylsulfonylethyltrimethylstannane, ##STR84## was subjected to similarhumidity conditions in the same equipment. The following samples of theindicated compound, purified by column chromatography, were weighed intosmall petri dish covers and placed in the 81% humidity chamber at atemperature of 27° C.: Dish #15 0.2426 g; Dish #34 0.2020 g. Over theperiod of the test, the temperature was maintained at room temperature.The #34 sample was removed from the chamber after 4 days and an infraredspectrum was run within several minutes. This showed no additionalabsorption bands from those of the starting material. The #15 sample wasremoved from the chamber after 2 weeks. The infrared spectrum of thissample was superimposable with the spectrum of the starting material. Noadditional absorption bands were present. The NMR spectra for bothsamples were identical to that for the starting material. It is thusestablished that the tested compound of this invention is not subject tohydrolysis under the stated conditions.

The following represents an attempt to follow the general procedure ofU.S. Pat. No. 3,794,670 of Peterson for the preparation of a compound ofthis invention, 2-[p-t-butylphenylsulfonyl]ethyltrimethylstannane,##STR85## However, the compound obtained is shown to be1-[p-t-butylphenylsulfonyl]ethyltrimethylstannane, ##STR86## Thissuffers from the same hydrolysis deficiencies as does the Petersoncompound of the preceding Example.

EXAMPLE 19

The equipment utilized was a 500 ml 3-necked round bottom flask fittedwith mechanical stirrer, N₂ inlet with Y-tube, 125 ml addition funnel(flame dried and N₂ filled) and ice water bath; for later use: simpledistillation take-off, thermometer and oil bath. The materials usedwere:

(1) 140.0 ml (total volume) reagent benzene distilled to remove waterazeotrope.

(2) 18.5 ml (13.1 g, 0.18 mole) diethylamine (dried).

(3) 94.0 ml (0.15 mole) 1.6 molar n-butyllithium in n-hexane.

(4) 29.8 gm (0.15 mole) trimethyltin chloride.

(5) 33.9 gm (0.15 mole) p-t-butylphenylethylsulfone (mol. wt. 226.3).

All syringes used were previously oven dried at 110° C. and cooled underN₂. The diethylamine (via syringe) + 50 ml of benzene (via syringe) wereintroduced into the flask. The butyllithium was placed into the additionfunnel (via syringe). The reactio flask was cooled with mechanicastirring using the ice water bath and the butyllithium was addeddropwise over a period of 33 minutes. The reaction solution was nowmilky white. The addition funnel was rinsed with 10 ml of benzene (viasyringe) and drained directly into the reaction flask. Into a N₂ flushed125 ml Erlenmeyer flask the trimethyltin chloride was weighed out anddissolved in 50 ml of benzene (via syringe) and poured into the additionfunnel (via syringe). An additional 25 ml benzene was used to rinse theflask, and was then added to the addition funnel. While keeping thereaction mixture at 0°-5° C. with the ice bath, the tin chloridesolution was added dropwise over a period of 1 hour. The reactionmixture was then allowed to warm to room temperature with stirring for 1hour and 10 minutes. The sulfone was weighed out and added directly as asolid, and readily disslved. The mixture was stirred for 1/2 hour atroom temperature and kept overnight under N₂. The reaction mixture was amilky light tan.

In the morning, the apparatus was adapted for distillation -- using animmersion thermometer, reflux thermometer, oil bath thermometer plusjoint and condenser and a 300 ml flat bottom 1-neck receiver flask --all under nitrogen.

                                      Table VIII                                  __________________________________________________________________________            Oil Bath                                                                             Internal Pot                                                                         Reflux                                                  Elapsed Time                                                                          Temperature                                                                          Temperature                                                                          Temperature                                             __________________________________________________________________________    Start   54     37.5   24     (R.T.)                                           15 mins.                                                                              69     55.0   24                                                      22 mins.                                                                              84     64     49↑                                                                            (Distillate coming over into receiver)           25 mins.                                                                              86     66     54                                                      35 mins.                                                                              83     73.5   61.5                                                    46 mins.                                                                              95.5   77     70     (Schlieren effect present in receiver)           1 hr. 5 mins.                                                                         100    83     72     (Schlieren effect present in receiver)           1 hr. 45 mins.                                                                        110    95     73                                                      2 hrs.  117    105    75.5                                                    2 hrs. 15 mins.                                                                       123.5  112    70     (Take-off decreasing)                            3 hrs. 20 mins.                                                                       125    115    50.5   (Ceased. Pot contents cloudy; brown slurry)      3 hrs. 55 mins.                                                                       125    115    60     (Stirring slowed; some drops over)               4 hrs. 5 mins.                                                                        125.5  115.5  49     (Occasional drops)                               4 hrs. 15 mins.                                                                       124.5  115.5  44                                                      4 hrs. 50 mins.                                                                       123    113    43     (Start N.sub.2 sweep through reaction flask                                   to receiver and refluxed back to                                              66°.                                                                   Pot temp. to 111° and distillate                                       coming over.)                                    5 hrs. 5 mins.                                                                        123    113    57.5   (Occasional drops)                               5 hrs. 15 mins.                                                                       123.5  114    51     (Occasional drops; let cool to R.T. under                                     N.sub.2.)                                        __________________________________________________________________________

The distillation apparatus was disassembled when cool. The receiver waskept under N₂ with stirring, and cooled down to 0°-5° C. with ice bath.A thick, light brown slurry resulted. 4.0 gms (3.4 cc, 0.04 mole) HClwas added to 200 cc H₂ 0 and the resulting solution was added slowly tothe receiver. At first, the pot temperature rose to 30°-35° C. andrapidly subsided. The rest of the HCl solution was added. The ice bathwas removed; 2 phases formed: a clear upper H₂ O and light brown viscouslower oil layer. 100 cc CHCl₃ were added to the pot to dissolve the oil,and the whole was transferred to a 1 liter separatory funnel; 100 mladditional CHCl₃ were added. Most of the organic layer was decanted. Theremaining organic and H₂ O layers were washed twice with CHCl₃, theresulting organic layers being decanted. The entire combined organicphase was dried over anhydrous MgSO₄ overnight. The whole was vacuumfiltered using a 15 cm Buchner filter,--keeping covered and avoiding airsuction through the funnel to avoid moisture contact. The slightlyturbid filtrate was treated with Darco G 60 at room temperature forabout 1.5 hours and gravity filtered (kept covered) into a tared 1liter, 1-neck round bottom flask, and the CHCl₃ was stripped on aRotovac (Rotovac vented under N₂) leaving a clear brown, slightlyviscous liquid having crude yield of 46.2 gms.

TLC (thin layer chromatography) on silica gel (Eastman) (9/1 volumeratio cyclohexane / EtOAc) showed two large spots with distances fromthe origin of 25 mm and 37 mm. The shorter distance spot had the samedistance as that for the starting ethylsulfone. The spots wereapproximately of equal size and intensity when observed under short waveU.V. The oil was subjected to vacuum distillation through a short pathhead using a single 50 ml receiver. An oil was collected between120°-154° C. at 0.06-0.12 mm Hg. The pot temperature ranged between 150°and 200° C. There appeared to be no separation points using this shortpath. The oil distillate formed some solid which was isolated bydecantation of the oil and pressing the solid on filter paper: 3.86 g.The solid was recrystallized from petroleum ether, m.p. 43°-65°. TLC ofthis material showed 2 spots the same as the crude product. Thedistillate oil was redistilled through a microware, vacuum jacketedVigreaux column. Cut #1: b.p. 48°-112.5° (2.5-3 × 10⁻³ mm). TLC showed alarge spot (starting sulfone) and a faint spot for product. Cut #2: b.p.108°-136° (2-8 × 10⁻³ mm). TLC showed a large spot for starting materialand a smaller one for product. Cut #3: b.p. 140°-145° (.01 mm) showedthe major component as product (faster moving component) and a smallerspot for starting sulfone. Cuts 1 and 2 were discarded as they had verylittle product. All three cuts were solids. Cut #3 weighed 5.6 g.

The solid from Cut #3 was taken into boiling petroleum ether andfiltered to remove cloudiness. The solution was concentrated to about 25ml and cooled in an ice-water mixture. The solid was pressure filteredunder nitrogen to give 2.78 g of white solid, m.p. 78°-81° C. The solidwas recrystallized from petroleum ether (about 10-15 ml) (cooled to -15°C.). The solid was filtered with a positive pressure of nitrogen to give2.21 g of a white crystalline solid, m.p. 79.5°-81.5° C.

The nuclear magnetic spectrum showed that there is a typical1,4-disubstituted aromatic pattern with a relative intensity of 4protons, comprising a band centered at 7.75 δ due to the two protonsortho to the SO₂ group and its mirror image centered at 7.47 δ due tothe two protons ortho to the tertiary butyl group. A quartet of bandscentered at 2.84 δ , relative intensity of one proton, is due to themethine proton. The tertiarybutyl and the single methyl resonancesoverlap to form a band of relative intensity of 12 protons, thetertiarybutyl resonance appearing as a singlet centered at 1.35 δ andthe methyl resonance appearing as a doublet centered at 1.29 δ . Thereis a singlet at 0.37 δ (37 Hz) flanked by two small satellite doubletswith a total relative intensity of 9 protons. This band is due to thetrimethyltin group. The two sets of satellite doublets are due to thecoupling of the three methyl groups to the two isotopes of Sn -- Sn¹¹⁷and Sn¹¹⁹ -- with a nuclear spin of 1/2. Thus, the structure aspresented in the paragraph preceding this Example is confirmed.

The comparative data in the following table (Table IX) were obtained onCompound 13 of this invention, a Peterson compound(trimethylphenylsulfonylmethylstannane) and the Peterson hydrolysisproduct referred to above (trimethyltin hydroxide). The Petersoncompound was prepared in accordance with Example 1 of U.S. Pat. No.3,794,670, except that an equivalent amount of trimethyltin chloride wasused instead of trimethyltin bromide. The trimethyltin hydroxide wasprepared by the method set forth by J. G. A. Luijten, Rec. trav. chim.82, 1179 (1963).

The mite one-day residual test differed as follows from that set forthin Example 13. The plants were held in a growth chamber maintained at85° F., and were exposed to high intensity fluorescent lights for 14hour days. The recorded observations were made 3 days after loading themites.

The 3-day tobacco bud worm test on cotton differed as follows from thatset forth in Example 14. The plants used were 3 weeks old, and werecovered with cheesecloth during the test. Six replicates were used foreach test compound, with 1 worm per plant. The plants were infested withlarva 3 days after the spray application and the recorded observationswere made 6 days after the spray application. In both of these tests,the solutions were made in terms of millimoles/liter so that the resultswould be strictly comparable, since the compounds are of differentmolecular weights.

                                      Table IX                                    __________________________________________________________________________                   Mite One-Day Residual                                                                     Tobacco Bud Worm                                                  Control     % Control   % Feeding Reduced                                     (millimoles/liter)                                                                        (millimoles/liter)                                                                        (millimoles/liter)                                    0.6 0.3 0.15                                                                              0.6 0.3 0.15                                                                              0.6 0.3 0.15                           __________________________________________________________________________    Compound 13:                                                                   ##STR87##     98.4                                                                              100 73  100 83  83  98  92  88                              ##STR88##     44  14  18  66  0   40  90  52  73                             (CH.sub.3).sub.3 SnOH                                                                        9   34  7   66  16  16  81  69  50                             __________________________________________________________________________

the decided superiority of the compound of this invention over theclosest comparable Peterson compound and over the hydrolysis product ofthe latter is readily apparent.

While the invention has been described with particularity and in somedetail, it should be understood that it is susceptible to variouschanges and modifications that will occur to those skilled in the artwithout departing from the scope of the spirit of the invention.

What is claimed is:
 1. A method for controlling insects or insect pestscomprising applying to a locus subject to attack by insects or insectpests an effective amount for controlling insects or insect pests of anorganotin compound having the structural formula ##STR89## wherein: R'is hydrogen, hydroxyl, alkoxyl or a straight chain or branched alkylgroup having 1 to 5 carbon atoms;X is (a) --SO₂ R₁, R' being hydrogen,and wherein R₁ is piperidinoethylmethiodide; (b) --OR₇, wherein R₇ isepoxyalkylene having 2 to 4 carbon atoms, andtetrahydro-1,1-dioxo-3-thienyl; (c) --SR₁₀, R' being hydrogen, andwherein R₁₀ is piperidinoethylmethiodide; (d) 2-pyridyl; (e) 4-pyridyl;(f) 2-alkyl-5-pyridyl; (g) 9-carbazolyl; (h) 1-imidazolyl; (i)N-2-oxopyrrolidinyl; (j) -OCOR₁₇, wherein R₁₇ is --NHR₁₈, wherein R₁₈ is2-furyl; (k) tetrahydro-1,1-dioxo-2-thenyl; ##STR90## wherein R₂ ispolymethylene having 2 to 11 carbon atoms; and n is an integer from 1 to10.
 2. The method of claim 1, wherein said organotin compound isselected from the group consisting of2-(2-piperidinoethylsulfonyl)ethyltrimethylstannane methiodide,3-(2,3-epoxypropoxy)propyltrimethylstannane,3-(tetrahydro-1,1-dioxo-3-thienyloxy)propyltrimethylstannane,2-(N-carbazolyl)ethyltrimethylstannane,trimethyl-2-(2-oxopyrrolidinyl)-ethylstannane,2-(N-imidazolyl)ethyltrimethylstannane,3-(2-furoyloxy)propyltrimethylstannane,2-(2-pyridyl)ethyltrimethylstannane,2-(2-methyl-5-pyridyl)ethyltrimethylstannane,2-(4-pyridyl)ethyltrimethylstannane,4-(tetrahydro-1,1-dioxo-2-thienyl)-3-hydroxybutyltrimethylstannane and2,2'-[2,4,8,10-tetraoxaspiro 5.5undec-3,9-ylene]-bis(ethyltrimethylstannane).
 3. The method of claim 2,wherein said organotin compound is2-(2-piperidinoethylsulfonyl)ethyltrimethylstannane methiodide.
 4. Themethod of claim 2, wherein said organotin compound is3-(2,3-epoxypropoxy)propyltrimethylstannane.
 5. The method of claim 2,wherein said organotin compound is3-(tetrahydro-1,1-dioxo-3-thienyloxy)propyltrimethylstannane.
 6. Themethod of claim 2, wherein said organotin compound is2-(N-carbazolyl)ethyltrimethylstannane.
 7. The method of claim 2,wherein said organotin compound istrimethyl-2-(2-oxopyrrolidinyl)ethylstannane.
 8. The method of claim 2,wherein said organotin compound is2-(N-imidazolyl)ethyltrimethylstannane.
 9. The method of claim 2,wherein said organotin compound is3-(2-furoyloxy)propyltrimethylstannane.
 10. The method of claim 2,wherein said organotin compound is 2-(2-pyridyl)ethyltrimethylstannane.11. The method of claim 2, wherein said organotin compound is2-(2-methyl-5-pyridyl)ethyltrimethylstannane.
 12. The method of claim 2,wherein said organotin compound is 2-(4-pyridyl)ethyltrimethylstannane.13. The method of claim 2, wherein said organotin compound is4-(tetrahydro-1,1-dioxo-2-thienyl)-3-hydroxybutyltrimethylstannane. 14.The method of claim 2, wherein said organotin compound is2,2'-[2,4,8,10-tetraoxaspiro 5.5undec-3,9-ylene]bis(ethyltrimethylstannane).